Deep research on electronic special gas industry in semiconductor industry chain

Electronic special gas: the blood of electronic industry

Special gases mainly include high-purity gases, electronic gases and standard gases. Electronic special gases (referred to as electronic special gases) are an important branch of special gases, and are indispensable raw materials for electronic industry production, such as ultra large scale integrated circuits (IC), flat panel display devices (LCD, led, OLED), solar cells, etc.

Generally, in semiconductor industry, gases are divided into common gases and special gases. Among them, commonly used gases refer to gases that are supplied and used in a centralized way, such as N2, H2, O2, AR, he, etc. Special gases refer to some chemical gases used in semiconductor production processes, such as extension, ion implantation, mixing, washing and mask formation, that is, electron gases in gas categories, such as high-purity SiH4, PH3, AsH3, B2H6, N2O, NH3, SF6, NF3, CF4, BCl3, BF3, HCl, Cl2, etc In the production process, more than 100 kinds of electronic gases are used, and about 30 kinds are common in the core section. It is these gases that make silicon wafers have semiconductor properties through different manufacturing processes. It also determines the performance, integration and yield of integrated circuits. Even if a certain impurity exceeds the standard, it will lead to serious quality defects. In serious cases, the whole production line will be polluted or even completely paralyzed due to the diffusion of unqualified gases. Therefore, electronic gas is the key material in the manufacturing process, which is the "blood" of the electronic industry.

At present, most of China's electronic gas market is occupied by several international giants, and the high-end gas almost completely depends on imports. On the one hand, the price is expensive, and the inlet gas price is generally 2-3 times or even higher than that of domestic gas, which increases the manufacturing cost of IC industry and weakens the competitiveness of China's IC industry In the face of some core cutting-edge gas, overseas giants impose various blockades and restrictions on China, and the supply situation is affected by international relations, which poses a threat to China's national security and economic development. In addition, many electronic gases are dangerous chemicals, which have complicated import procedures, long cycle, unstable nature of some electronic gases, spontaneous decomposition, strong corrosion, long-time storage, and high impurity content. Therefore, it is inconvenient to import them across the sea. To sum up, the development of independent production of electronic specialty gas in China can improve the integrated circuit industry chain, which has great practical and far-reaching strategic significance.

The standard commonly used for electronic gas in the world is semi standard (international semiconductor equipment and materials committee standard), but several foreign gas companies have their own company standards. These standards highlight the technical level of each company, and the purity of products is generally 1-2 orders of magnitude higher than semi, It has its own characteristics in the aspects of analysis and detection, packaging, use method, application technology description, etc. some companies only indicate "need to negotiate with users" on the content of some key impurities (metal impurities, particulate matter impurities, etc.), which indicates that the electronic gas technology and market competition are very fierce, and the key technologies are confidential.

According to the different composition and application, electronic special gases can be roughly divided into seven types: doping gas, epitaxial crystal growth gas, ion implantation gas, etching gas, CVD gas, equilibrium / reaction gas and doping formula gas. Among them, some special gases are used in many links (such as silane). The breakdown categories of various electronic specialty gases are shown in the table below.

According to statistics, electronic specialty gas accounts for about 14% of the material cost in the wafer manufacturing process, which is the second largest material after silicon wafer. According to China electronic news, the overall market scale of domestic wafer manufacturing materials in 2018 is about US $2.82 billion; packaging materials include lead frame, substrate, ceramic packaging materials, bonding wire, packaging resin, chip mounting materials, etc., and the market scale of domestic packaging materials in 2018 is about US $5.68 billion. In 2018, the total market size of wafer manufacturing materials and packaging test materials is about US $8.5 billion. In terms of electronic special gas, the market scale of electronic special gas for semiconductor in China in 2018 was about US $489 million. After more than 30 years of development, China's semiconductor electronic special gas has achieved good results. China Shipbuilding 718 Institute, Lvling electronics and Guangdong Huate have made breakthroughs in 12 inch wafer products, and achieved stable batch supply. In May 2018, China Shipbuilding 718 Institute held the commencement ceremony of the second phase project. After the completion of the project in 2020, it will produce 20000 tons of high-purity electronic gas annually. The production capacity of nitrogen trifluoride, tungsten hexafluoride, hexafluorobutadiene and trifluoromethylsulfonic acid will rank first in the world. In terms of high-purity silane, Zhongning silicon industry uses self-produced high-purity silane as raw material to research and develop low-temperature light and heavy removal, multi-stage adsorption and crystalline silicon film-forming detection technologies with independent intellectual property rights to prepare semiconductor grade silane gas. It has achieved breakthroughs in key technologies such as equipment optimization, distillation purification and film-forming detection, and has the industrial production capacity of semiconductor grade silane gas power. In terms of high-purity silicon tetrafluoride, the products of Lvling electronics have achieved large-scale supply to major domestic chip manufacturers in 2018.

The upstream of electronic special gas is mainly the basic chemical industry of III (boron, aluminum, gallium), IV (carbon, silicon, germanium), V (nitrogen, phosphorus, arsenic) and halogen (fluorine, chlorine), while the downstream has various uses in various process links of integrated circuit, panel, LED and other fields.

Similar to the technical drugs and preparations in the pesticide industry, the special gas industry is also divided into raw material gas and filling gas. In general, the feed gas is a single product with high purity, and the filling gas after compounding is usually used by downstream customers.

High purity requirements, purification, impurity detection, storage and transportation technology is facing a comprehensive test

The electronic special gas industry itself can be divided into two parts: synthesis and purification. Due to the continuous progress of IC production process and technology, the chip size is gradually improved, the process is gradually improved, and the characteristic size and linewidth are gradually reduced. Some electronic gases that need to be used in IC process have higher quality, the specified technical indicators are gradually improved, and the demand for core impurities is also more stringent. Even if one of the special impurities does not meet the requirements, it will make the IC quality have great problems, become defective or waste products, and even cause the whole production line pollution because of the gas diffusion that does not meet the requirements. If there are metal impurities, it will make the positive charge or silicon dioxide surface transition, making the IC characteristics change, and it will lead to the device gradually lose its function, reduce its service life, and bring negative effect on the reliability of the component. When there are particles, it will also lead to surface problems, which will greatly affect the working stability, and seriously will lose its function.

The 12 inch and 90 nm IC manufacturing technology requires that the purity of electronic gas should be above 99.999% - 99.9999% (5n-6n), and the harmful gas impurities should be controlled at 10-9 (ppb), which makes strict restrictions on metal impurities and dust particles. In the more advanced 28nm process and the current international first-line 6nm-10nm process, the purity requirement of electronic special gas is likely to be higher, even up to ppb (10-12) level. Due to the industry's special requirements for product purity, the purification, impurity detection, storage and transportation technology of electronic special gas is facing a comprehensive test. In the aspect of impurity detection, because the impurity content to be detected is as low as ppb level, the conventional analysis method is not competent, so special unconventional analysis methods such as gas chromatography, ICP-AES and ICP-MS are needed; in the aspect of storage and transportation, on the one hand, due to the high purity requirement, the dissolution performance of the container is put forward On the other hand, some highly toxic gases need to be stored in negative pressure cylinders to reduce the risk of leakage.

Low temperature distillation, membrane separation and adsorption separation are the main purification technologies

At present, low temperature distillation, membrane separation, adsorption separation and absorption are the main preparation methods of electron gas.

Cryogenic distillation

This technology is the main gas separation and purification technology used by most high purity electronic gas suppliers, and its industrial application is quite mature. Low temperature distillation is to liquefy the mixture of some gases by freezing. It depends on the difference of relative volatility between two or more gases and distills by changing temperature or pressure. This separation method is simple and suitable for the removal of some non condensable gases in gas mixture, such as nitrogen, hydrogen, oxygen and other compressed gases.

High purity BF3 is mainly purified by low-temperature distillation. The process is shown in the figure below. The specific setting of the low-temperature distillation column is that the temperature in the middle of the distillation column is about - 96 ℃, and the temperature in the lower part is about - 98 ℃. BF3 enters the rectifying tower. By controlling the temperature of rectifying tower, BF3 enters the condenser in the form of gas from the upper end of rectifying tower, while SiF4 enters the reboiler in the form of liquid from the bottom end, so as to carry out low-temperature rectification operation and realize the separation of two substances. However, this method has large energy consumption and strict operating conditions.

Adsorption separation technology

Adsorption separation technology has become a widely used method in industry, and adsorption can be divided into chemical adsorption and physical adsorption. Zhaohe Electric has disclosed a production method of adsorbent for purification of perfluoroalkane hydrocarbons such as octafluoropropane and octafluorocyclobutane. The adsorbent can effectively absorb hexafluoropropylene, pentafluoroethane, heptafluoropropane and other impurities in octafluoropropane, and reduce the impurity content to 1 × 10-6. The main steps are as follows: 1) acid washing and water washing of raw carbon; 2) deoxidation or dehydration of raw carbon at 50-250 ℃; 3) carbonization of raw carbon at 500-700 ℃; 4) activation of raw carbon in inert gas, carbon dioxide and water steam mixture at 700-900 ℃. The purity of octafluoropropane after purification by the adsorbent can be more than 6N (99.9999%).

Membrane separation technology

Membrane is a kind of selective separation material. The process of membrane separation is called membrane separation, which is used to separate, purify and concentrate the different components in raw materials.

The core of membrane separation technology is membrane material, and membrane material is the key to the development of membrane separation technology. Since the high tide of gas separation membrane research was launched in 1970s, almost all available and film-forming polymer materials such as PDMS, PSF, Ca and PC were evaluated in gas separation. The common problems are: for the films with high permeability, the selection coefficient is low; For the membrane with high selection coefficient, its permeability coefficient is low. Therefore, in order to obtain the membrane materials with high quality, it is necessary to synthesize the special gas separation membrane polymer.

Dagin patent reported a technology of removing CO2 from COF2 by gas separation membrane. This method has become one of the possible means to reduce CO2 content in high purity carbon acyl fluoride project. The high purity carbon fluoride can be obtained by refining and purifying the carbon acyl fluoride by using the technology of Polyimide Hollow fiber membrane. The membrane separation device is shown in the following figure. The hollow fiber membrane used is polyimide membrane, which can be selected from Kapton (DuPont), citrimid (cibageigy), um, DM (Yubu production) series. Hollow fiber membrane needs to be made by ourselves. Before use, the factors that may affect COF2 caused by H2O and O2 in the device are removed by the flow regulator 2. The pressure difference between the through side and the non penetrating side of the hollow fiber membrane separating the gas is 0.01-1.00 MPa and the temperature is 0-50 ℃.

Negative pressure cylinder technology is necessary for the storage and transportation of dangerous special gas

In the process of semiconductor manufacturing, harmful and toxic gases are often used. Although the density of gas storage and transportation in traditional high-pressure cylinder is high enough, once the cylinder is in high-pressure state, accidental release or leakage will lead to the escape of highly toxic, flammable and explosive dangerous gas Therefore, for those highly toxic or dangerous gases, high-pressure cylinder is no longer a suitable way of storage and transportation, and negative pressure cylinder technology has gradually replaced and become the industry standard. The negative pressure cylinder technology uses the substrate with nano holes to absorb gas molecules, so that the pressure of the cylinder is reduced below the atmospheric pressure, thus reducing the risk of dangerous gas leakage.

In 1993, advanced technology materials, Inc. (ATMI) first applied and commercialized the negative pressure cylinder technology, with the trademark name of safe delivery source, namely SDS cylinder. Up to now, the use of SDS negative pressure gas cylinders for hazardous electron special gases such as phosphine, arsenane and boron trifluoride used in ion implantation has been mandatory. In 2014, Entegris acquired advanced scientific and technological materials, and now Entegris SDS storage technology products occupy 85% of the global market share of dangerous special gas storage and transportation.

The SDS system uses brightbrick as the adsorption material, which is a porous carbon material with a specific surface area of up to 500 square meters / g. filling brightbrick into a 1-2 foot high cylinder is called SDS negative pressure cylinder.

The overseas leading enterprises monopolize the market, and the domestic substitution is imminent

At present, the global electronic special gas market is monopolized by leading enterprises in several developed countries, and domestic enterprises are facing fierce competition. In terms of global market scope, the companies providing special electronic gases mainly include gas chemical industry of the United States, Praxair of the United States, Showa electric of Japan, BOC of the United Kingdom (acquired by Linde in 2006), Linde of Germany (merged with Praxair of the United States in 2018), air liquide of France, dayangri acid of Japan, etc. In the global special gas market, American air chemical, Praxair, faliquo, dayangri acid and German Linde occupy 94% of the global market share; several leading overseas enterprises in the domestic market also control 85% of the global market share, and the situation of electronic special gas being controlled by others needs to be changed.

The standard commonly used in the world for electronic gas is semi standard (international semiconductor equipment and materials committee standard), but several major foreign gas companies have their own company standards. These standards highlight the technical level of each company, and the purity of products is generally 1-2 orders of magnitude higher than that of other companies Some companies only indicate "need to negotiate with users" on the content of some key impurities (metal impurities, particulate matter impurities, etc.), which indicates that the electronic gas technology and market competition are very fierce, and the key technologies are confidential.

Semiconductor industry chain transfer to Chinese mainland, special gas market space expands rapidly.

In terms of semiconductor industry, according to WSTS statistics, the global semiconductor market space in 2018 was US $468.8 billion, of which US $282.9 billion was in the Asia Pacific region, accounting for 60%. In the global semiconductor market, the market space of IC industry is 393.3 billion US dollars, accounting for 84%. Due to Sino US trade frictions, WSTS has recently substantially revised down the growth rate of global semiconductor market in 2019 and 2020. It is estimated that the global semiconductor market will reach US $412.1 billion in 2019, down 12%, including US $255.7 billion in the Asia Pacific region, down 10%.

Under the background of great downward pressure on the global semiconductor industry, the high growth rate of China's semiconductor industry is facing a decline. From 2013 to 2018, the compound growth rate of sales of China's IC industry was as high as 21.1%, and the year-on-year growth rate in 2018 was still as high as 20.7%. However, according to the quarterly data, the growth rate of China's IC industry has dropped significantly since the third quarter of 2018, with the year-on-year growth rates of 26%, 20%, 17% and 11% in 2018q2, 2018q3, 2018q4 and 2019q1 respectively. Looking forward to the whole year of 2019, the growth rate of China's IC industry will still maintain high growth.

According to SEMI estimates, 62 semiconductor wafers will be put into operation in the world in 2017-2020, of which 26 are located in Chinese mainland, accounting for 42% of the total global market. The space of global wafer fabrication materials market has increased from US $22 billion 700 million in 2013 to US $32 billion 200 million in 2018, with an average annual growth rate of 7.2%. It will increase to US $4.1 billion by 2020.

According to our statistics, 2019-2020 is the intensive production period of China's mainland wafer plants. Based on the 12 inch equivalent capacity, the capacity of China's mainland wafer plants in 2018 will be 1.19 million pieces / month, and it will grow to 3.59 million pieces / month by 2021, with an average annual growth rate of 44%. Among them, the growth rate in 2019 and 2020 will be the fastest, reaching 59% and 67% respectively. The total capacity of the wafer plants put into operation in 2019 and 2020 will be 1.9 million pieces / month respectively 700000 and 1270000 tablets / month.

According to the publicity materials of Huate gas sales department, the value of electronic special gas consumed by the 8-inch wafer factory with a monthly production capacity of 50000 pieces in one year is about 50 million yuan. According to this calculation, the market space of electronic special gas for semiconductor in China will be about 2.7 billion yuan in 2018, and will grow to 8.1 billion yuan by 2021. See Table 7 for detailed categories of electronic special gas consumed by the 8-inch factory with a monthly production capacity of 50000 pieces.

Taking sun as a reference, the development trend of China's special gas demand

The pan semiconductor (chip + panel) industry in Japan has developed more mature and has a perfect special gas supply system. We speculate the development trend of special gas demand in China based on the demand change of Japanese electronic special gas and the development trend of Pan semiconductor industry in Japan and China.

It can be found that the composite growth rate of varieties with increasing dosage in advanced process, such as octafluorocyclobutane, is higher, which is consistent with the trend of continuous upgrading of semiconductor process; the varieties with low composite growth rate are mainly in ion implantation and CVD in many sets The gas is consistent with the trend of Pan semiconductor industry gradually shifting from Japan to Korea, China Taiwan and Chinese mainland.

In China, the demand of various electronic specialty gas varieties in China is increasing rapidly because the global panel and semiconductor industry are transferring to mainland China. The demand of ion implantation and CVD source gas in Japan is strong because of the low independent production capacity in China. The advanced process demand varieties such as octafluorocyclobutane and hexafluorobutadiene will also be increasing rapidly with the development of the process in China.

There is a large number of subdivided varieties, and there is a strong demand for import substitution of high-end varieties

Fluorine containing gas: traditional products are gradually controlled independently, and advanced technology and environmental protection gas are gradually catching up

At present, fluorine-containing electronic gases account for about 30% of the total electronic gases in the global electronic gas market. Fluorine containing electronic gases are an important part of special electronic gases in the field of electronic information materials. They are mainly used as cleaning agents, etching agents, dopants, film-forming materials, etc. Typical traditional fluorine-containing electronic gases include CF4, C2F6, C3F8, C4F8, CHF3, SF6, NF3, etc. due to the atmospheric lifetime of traditional fluorine-containing gases and GWP (global warming potential), the greenhouse effect of various greenhouse gases corresponds to the same effect of carbon dioxide in a 100 year time frame In recent years, the development of new, safe and environmentally friendly fluorine-containing electronic gases has become a research and industrialization hotspot at home and abroad. At present, the new low GWP fluorine-containing gases mainly include COF2, clf3, F2, etc.

In addition to environmental protection factors, advanced process technology also puts forward higher and higher requirements for etching gas: in advanced process and high aspect ratio process, unsaturated perfluoroelkenes, such as hexafluorobutadiene and octafluorocyclopentene, are usually used to replace traditional perfluoroalkanes and NF3, because hexafluorobutadiene and octafluorocyclopentene are more and more important The selectivity, accuracy and anisotropy of pentene are better.

The most important application of fluorine-containing electron gas is the etchant and cleaning agent used in dry etching. Because wet etching can only be used for more than 2 μ m, and it is isotropic etching, which leads to the formation of side slope. Therefore, dry etching is the mainstream process in the small feature size fine etching of advanced circuits. Fluorine containing electron gases such as CF4, C2F6, C3F8, C4F8, SF4 and SF6 are the main etchants in dry etching.

Tetrafluoromethane (CF4)

Tetrafluoromethane (CF4) is the most widely used plasma etching gas in microelectronics industry. It is widely used in the etching of silicon, silicon dioxide, silicon nitride, phosphorous silicon glass and other materials, such as surface cleaning of electronic devices, production of solar cells, laser technology, low temperature refrigeration, gas insulation, leakage detection agent, etc There are also a lot of applications in controlling space rocket attitude, detergent, lubricant and brake fluid in printed circuit production. Because of its strong chemical stability, CF4 can also be used in metal smelting and plastic industry. Nowadays, the characteristics and development trend of electronic gas used in VLSI are ultra pure, ultra clean, multi variety and multi scale. In order to promote the development of domestic microelectronics industry, countries pay more and more attention to the development of special electronic gas production technology. At present, CF4 occupies the etching gas market for a long time with its relatively low price, so it has broad development potential.

At present, the main methods of preparing CF4 in industry are alkane direct fluorination, chlorofluoromethane fluorination, hydrofluoromethane fluorination and fluorocarbon direct synthesis.

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Hexafluoroethane (C2F6)

Hexafluoroethane is used in semiconductor and microelectronics industry as plasma etching gas, device surface cleaning agent, optical fiber production and low temperature refrigeration. Because of its non-toxic, odorless and high stability, it is widely used in semiconductor manufacturing process, such as etching agent, cleaning gas after chemical vapor deposition (CVD), and dry etching gas of silicon dioxide and phosphorous silicon glass in plasma process. In recent years, with the rapid development of semiconductor industry, the purity of electronic special gas is required to be higher and higher. Hexafluoroethane has the advantages of minimal edge lateral erosion, high etching rate and high accuracy, which solves the problem that conventional wet etching can not meet the requirements of high-precision fine line etching of 0.18-0.25 μ m deep submicron integrated circuits, and can perfectly meet the requirements of this kind of linewidth Smaller process requirements. In various CVD processes based on SiH4, hexafluoroethane, as a cleaning gas, has the characteristics of low emission, high gas utilization rate, clean reaction chamber and high equipment yield compared with methane. High purity hexafluoroethane is a necessary medium for VLSI, which plays an important role in the development of semiconductor industry.

At present, there are many methods to prepare hexafluoroethane, including electrochemical fluorination, pyrolysis, metal fluoride fluorination, hydrogen fluoride catalytic fluorination and direct fluorination. ① Electrochemical fluorination: acetylene, ethylene or ethane are fluorinated under electrolytic conditions. ② Pyrolysis method: prepared by thermal decomposition reaction between tetrafluoroethylene and CO2. ③ Metal fluoride fluorination: for example, acetylene, ethylene and ethane react with metal fluorides (cof3, mnf3, agf2). ④ Hydrogen fluoride catalytic fluorination: fluorination of all halogenated ethanes (c2fxcly) in the presence of catalyst. ⑤ Direct fluorination: activated carbon, acetylene, ethane and pentafluoroethane react with fluorine directly.

At present, domestic manufacturers of semiconductor grade hexafluoroethane mainly include Huate Co., Ltd. and China Shipbuilding 718 Research Institute. Their existing capacity is 350 tons and 50 tons respectively, and their newly increased capacity is 100 tons and 60 tons respectively. The newly increased capacity of Huate Co., Ltd. is a project invested by science and technology innovation board, and the newly increased capacity of China Shipbuilding 718 Research Institute was announced in December 2018. In addition, Huaan new material has a capacity of 300 tons of hexafluoroethane, but it is mainly a refrigerant product. In addition, the joint-stock company of Juhua, Borui electronics, plans to build a capacity of 55 tons of hexafluoroethane, which will be announced in February 2019.

Nitrogen trifluoride (NF3)

Nitrogen trifluoride is mainly used for cleaning chemical vapor deposition (CVD) devices in semiconductor industry. Nitrogen trifluoride can be used alone or in combination with other gases as etching gas for plasma process. For example, NF3, NF3 / AR and NF3 / he are used for etching silicon compound MoSi2; NF3 / CCl4 and NF3 / HCl are used for etching MoSi2 and NbSi2.

Nitrogen trifluoride is an excellent plasma etching gas in microelectronics industry. For etching silicon and silicon nitride, nitrogen trifluoride has higher etching rate and selectivity than carbon tetrachloride and the mixture of carbon tetrachloride and oxygen, and has no pollution to the surface, especially in the integrated circuit with thickness less than 1.5um In the etching of road materials, nitrogen trifluoride has excellent etching rate and selectivity, leaving no residue on the surface of the etched object, and it is also a very good cleaning agent. There are two main preparation methods of nitrogen trifluoride: direct method and ammonium hydrogen fluoride molten salt electrolysis method.

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Sulfur hexafluoride (SF6)

As an important fluorine-containing gas material, sulfur hexafluoride is widely used in power equipment industry, semiconductor manufacturing industry, refrigeration industry, nonferrous metal metallurgy, aerospace, medical (X-ray machine, laser machine), meteorology (tracer analysis), chemical industry and other industries and fields. As sulfur hexafluoride has excellent insulation performance and arc reduction ability, industrial sulfur hexafluoride is widely used in power transmission, distribution and control equipment industry, including gas insulated switchgear, circuit breaker, high-voltage transformer, insulated transmission line, high-voltage switch, gas sealed combined capacitor, transformer, etc The third generation of insulating medium after the second generation of oil. Electronic grade sulfur hexafluoride is mainly used for etching and cleaning in the production process of semiconductor and panel crystal display devices. It has the characteristics of low consumption, high purity, high requirements for the cleanliness of production and use environment, and fast product upgrading. There are only a few furniture factories in China that have the capacity to produce furniture.

In industry, sulfur hexafluoride is usually prepared by the reaction of fluorine produced by electrolysis with sulfur at medium and high temperature. The main production process is to produce F2 by electrolysis of anhydrous hydrogen fluoride in an electrolytic cell, which reacts with elemental sulfur added into a reactor, and then decomposes the toxic by-product s2f10 at 350 ℃ through a pyrolysis tower, and then removes it by water washing and alkali washing HF, F2 and other impurities enter the low-pressure adsorption to remove water, high-pressure adsorption to remove acid gas, distillation at - 30 ℃ to remove air and low boiling point gas, SF6 escaping through the tail gas trap (- 60 ℃) for capture and filling.

KEMET, a subsidiary of yak technology, is the leader of sulfur hexafluoride in China, and now has a capacity of 7000 tons of SF6. In February, 2018, the company announced the EIA of the expansion project, and it is proposed to add 10000 tons of electronic SF6 and 2000 tons of CF4 capacity. After the expansion, the company will further consolidate its leading position in China. In addition to comet, liming Institute, a subsidiary of Haohua technology, a listed company, has 2800 tons of SF6 capacity, and the new capacity of 2000 tons is in the EIA review stage at the end of 2018.

Tungsten hexafluoride (wf6)

Tungsten hexafluoride (wf6) is the only stable and industrialized product of tungsten fluoride. Its main purpose is to be used as raw material for CVD process in electronic industry, especially WSi2 made from it can be used as wiring material in LSI. It can also be used as raw materials, fluorinated agents, polymerization catalysts and optical materials of semiconductor electrodes

With the continuous development of electronic industry, the world's major companies have expanded the capacity of wf6 since the end of 1990s. The high precision of electronic industry products has put forward high requirements for the purity of wf6 as raw materials. Generally, the purity is 99.99%, and the purity of some semiconductor industries is higher.

The synthesis method of tungsten hexafluoride is relatively simple in principle. It can be obtained by direct reaction of tungsten with fluorine gas or nitrogen trifluoride

W+3F2→WF6

W+2NF3→WF6+N2

The crude wf6 may contain N2, HF, SF6, CF4, mof6, CO2, Co, water and some impurities of metal particles. After being removed by distillation and adsorption, the pure tungsten hexafluoride can be obtained.

Currently, domestic wf6 manufacturers mainly include 718 pirit gas and Nantong Houcheng, a subsidiary of Korea Hou Cheng, and subsequent expansion plans for perritte gas and Borui zhongnit.

Octafluoropropane (C3F8)

Octafluoropropane (C3F8, also known as perfluoropropane, R218) is a stable perfluorocarbon. It is a colorless gas in the standard state, and its solubility in water and organic matter is very small. In semiconductor industry, the mixture of octafluoropropane and oxygen is used as plasma etching material, which selectively acts with the metal matrix of silicon wafer. With the rapid development of electronic industry, the demand of high-purity octafluoropropane is increasing. Because of the more and more precise requirements for etching precision, the purity requirements of the high-purity octafluoropropane are also higher and higher. At present, the purity of high-purity octafluoropropane electronic gas in the market is more than 99.999%. In addition, the use of octafluoropropane in medical field has been developed in recent years. It is mainly used in acoustic ultrasound. Octafluoropropane microbubbles can reflect sound waves and enhance the backscattering of ultrasonic signals. It has enough time to stay in the blood vessels, and can be used as a blood ball tracer to reflect the perfusion of organs without interfering with hemodynamics. In addition, octafluoropropane can be used as the medium for the deep cooling and heat exchanger.

There are two main preparation processes of octafluoropropane, one is hexafluoropropylene addition, one is the by-product of other fluorocarbon gas, and the other is the by-product when preparing CF4.

Currently, the main domestic perfluoropropane producers are 718 pirit gas and nuclear industry physical and chemical engineering researchers participating in Sichuan Fuhua Xin, which have 30 tons and 200 tons of production capacity respectively. In addition, Huate Co., Ltd. plans to increase the capacity of 100 tons of octafluoropropane in the project.

Octafluorocyclobutane (C4F8)

Octafluorocyclobutane is a kind of green and environmental friendly special gas with stable chemical properties, non-toxic and harmless, low GWP and zero ODP. Eight fluoro butane has been widely used in recent years. It has been widely used as refrigerant instead of banned chlorofluorocarbons. In addition, it is also widely used in gas insulating medium, solvent, spray, foaming agent, large scale circuit etchant, heat pump working fluid and raw materials for producing C2F4 and C3F6 monomers. High purity octafluorocyclobutane (5N or more) is used for etching and cleaning agents for VLSI. For the preparation and purification of octafluorocyclobutane, the research abroad started earlier, such as DuPont company, Japan Daikin Industrial Co., Ltd., Japan Zhaohe Electric Co., Ltd., Japanese sunitro subsidiary, and Russian kilov plant, etc. With the rapid development of chemical and electronic industries in China, the demand of octafluorocyclobutane has increased year by year. The research on the preparation and purification process of octafluorocyclobutane has attracted more attention and has a wide application prospect.

The main manufacturing process of octafluorocyclobutane is tetrafluoroethylene dimerization, that is, the tetrafluoroethylene is used as raw material, and the pipe or kettle reactor is used as the polymerization inhibitor, and dimethyl sulfate, ethylene, ammonia or terpene are used as polymerization inhibitor, and polymerized at 400-750 ℃, 0.005-0.1 MPa.

In addition to the mainstream process, Chenguang Institute of Haohua science and technology has disclosed a method for recovering octafluorocyclobutane from the residual liquid of tetrafluoroethylene production process, which can obtain octafluorocyclobutane with a purity of more than 99%. The conventional distillation unit and extractive distillation unit are used in the method, and the extractant is commonly used. The operation is easy to realize, the cost is low, and the recovery rate of residual liquid is more than 99% 90%, suitable for industrial production.

At present, the main producers of octafluorocyclobutane in China include Showa Electronics (Shanghai), perritte gas (718 institutes), Huate Co., Ltd. and Baoding North gas. Showa electronics and perritte gas have the capacity of 150 tons and 50 tons of octafluorocyclobutane respectively, and perritte gas has the capacity expansion plan of 220 tons, which is expected to be put into production in June 2020. Huate shares did not disclose octafluorocyclobutane as the main product in the prospectus, so the capacity scale should be small; Baoding Beifang special gas is not a listed company, and the specific capacity has not been disclosed.

Hexafluorobutadiene (perfluorobrene, C4F6)

Hexafluorobutadiene, also known as perfluorbutadiene, was synthesized as a monomer of polymer at first, but its polymer performance was not good, and it has not been further studied and applied. In recent years, the application of hexafluorobutadiene has been focused on its use as an electron etching gas.

Hexafluorobutadiene and octafluorocyclopentene (C5F8) are considered to be competitive gases in the next generation, especially C4F6, which can replace CF4 for KrF laser sharp etching of semiconductor capacitor. C4F6 has many advantages in etching in advanced process technology: it has high selectivity, accuracy and anisotropy, and is suitable for etching electronic circuits below 100 nm, and has better performance than perfluorocarbon gas and NF3; C4F6 and C4F8 has higher selection ratio to optical resistance and silicon nitride, which is two important advantages; in addition, environmental aspect is also a very important factor, and C4F6 has a global warming potential value (GWP) of almost 0. Experts point out that C4F6 may be the only alternative to provide the required etching conditions and reduce emissions so far

The synthesis route of hexafluorobutadiene is diversified, but the core intermediates can be divided into six fluorine tetrachloroprene (cf2cl-cfcl-cfcl-cf2cl), octafluorodibromo (iodine) butane (cf2brcf2cf2cf2br, cf2brcf2cf2cf2i), trifluoroethylchloride (bromine) The three main types of zinc (CF2 = cfzncl, CF2 = cfznbr) are used as the starting materials for chlorohydrocarbons such as tetrachloroethylene, trichloroethylene and trichloromethane, and fluorine containing substances such as HF and F2.

Hexafluorotetrachloroprene method: after the core intermediate cf2cl-cfcl-cf2cl is obtained, hexafluorobutadiene can be obtained by dechlorination with zinc powder. The conditions are mild and the yield is 93-98%. In the early stage, the intermediate hexafluorotetrachloroprene was synthesized by direct dimerization of dichlorodifluoroethylene (dcdf) initiated by fluorine gas at low temperature, with a yield of 30-50%. Then, a three-step process of high temperature dimerization, chlorine greening and triple antimony dichloride (sbf3cl2) fluorination was developed, the yield was increased to 78%, but the reaction rate of high temperature dimerization was slow, which restricted the production efficiency of the method. Difluoroethylene is mainly made from R112 (difluoroethane) by dechlorination with zinc powder, while R112 is a byproduct of R113 (trifluoromethylethane), and its source is limited.

In order to solve the problem of limited source of R112, a new synthesis method based on R113 was developed, namely, R113 was dechlorinated by zinc powder to obtain trifluoro-chloroethylene, then added iodine chloride to obtain trifluoro dichloroiodoethane, and then hexafluorotetrachloropane was obtained by light coupling under mercury catalysis. The later improvement was made Methods the coupling reaction was carried out by zinc / acetic anhydride or zinc / ethyl acetate system, and the yield was 70% and 97% respectively.

Octafluorodibromodiobromo (iodine) butane method: octafluorodibromobromobutane or octafluorodiiodine can directly get hexafluorobutadiene by de halogenation of butyl lithium, with a yield of 97%. However, because of the danger and expensive of butyl lithium, this method is not practical. The research on dehalogenation process of octafluorodibromo (iodine) butane was mainly focused on the use of zinc, magnesium metal, its auxiliaries and solvents, and achieved good results. Octafluorodibromodibromo (IODE) butane can be obtained by the reaction of tetrafluoroethylene with tetrafluoroethylene.

Zinc trifluoroethylchloride (bromo) method: zinc trifluoroethylchloride (bromo) can be coupled to hexafluorobutadiene under the action of catalyst. The typical method for the synthesis of CF2 = cfznx (x=br, CL) intermediate is to isomerize 1,2-dibromoethane into 1, After 1-dibromoethane, zinc powder is added to DMF, and it can be synthesized by adding zinc powder into trifluoroethylene to trifluoroethylene, while trifluoroethylene can be synthesized by high temperature dehydluorination of R134a or hydrofluoroethylene. It is also the main by-product of the synthesis of trifluoroethylene.

At present, there are few domestic producers of hexafluorobutadiene, and the supply is mainly concentrated in the hands of overseas manufacturers and their domestic subsidiaries. The Houcheng Nantong subsidiary of South Korea has a production capacity of 40 tons of hexafluorobutadiene. The project was announced in the environmental impact assessment in 2017, and it is speculated that it has been put into production; among the projects under construction, 718 of them are dispatched Ruite gas, Borui electronics and meissel gas, a subsidiary of German meissel group, have capacity of 200, 50 and 45 tons respectively.

New fluorine-containing gas

Due to the high atmospheric lifetime and GWP (global warming potential) of traditional fluorine-containing gases, the greenhouse effect of various greenhouse gases corresponds to the quality of carbon dioxide with the same effect in a 100 year time frame, which causes great damage to the ozone layer Facing the gradual reduction or even prohibition within the framework, the development of new, safe and environmentally friendly fluorine-containing electronic gases has become a research and industrialization hotspot at home and abroad in recent years. At present, new low GWP fluorine-containing gases mainly include COF2, clf3, F2, etc.

Carbonyl fluoride: as a new generation of cleaning and etching materials for industrial semiconductor equipment, carbonyl fluoride has extremely low global warming potential (GWP ≈ 1), extremely low ozone layer destruction potential (ODP = 0), and extremely low atmospheric lifetime (< 1a). It is an environment-friendly electron gas. In addition, it can react with water to generate CO2, so there is no need for complex waste gas treatment process in practical application, so it has a broad application prospect.

As early as 2005, Daikin has planned to use it in semiconductor chemical gas deposition (CVD) cleaning equipment. Since 2011, Japan's well-known fluoride production companies such as Kanto chemical and Showa electric have built high-purity COF2 production plants, of which the annual output of COF2 in Kawakawa plant of Kanto chemical has reached 1000 tons. The synthesis methods of COF2 are mainly divided into four categories: ① Co or CO2 as raw material, and F2 reaction; ② phosgene as raw material and F2 reaction; ③ trifluoromethane or chlorodifluoromethane as raw material; ④ tetrafluoroethylene as raw material and O2 reaction. Among them, phosgene is more toxic, trifluoromethane and chlorodifluoromethane are forbidden greenhouse gases, and the cost of tetrafluoroethylene as raw material is higher, so the synthesis of COF2 with CO as raw material is more widely used.

There is no large-scale industrial production of carbonyl fluoride in China. Sichuan fuhuaxin, a subsidiary of the Institute of physical and chemical engineering of nuclear industry, has carbonyl fluoride products for sale, but the purity and production scale of the products are unknown. China Shipbuilding 718 Institute has applied for a certain number of preparation patents, and has small-scale pilot production. In addition, the new third board has been listed Sinochem modern environmental protection Chemical Co., Ltd., a joint venture of Sinochem Group and Xi'an Institute of modern chemistry, published a paper on the preparation of carbonyl fluoride.

Because of its unique chemical structure, the chemical activity of chlorine trifluoride tends to fluorine, but it is much milder than fluorine, and more environmentally friendly than fluorocarbons. Its GWP value is zero, so it is regarded as an ideal LPCVD cleaning gas. Japan's Kanto chemical industry, central Asahi nitiko industry and IWAYA industry have produced high-purity clf3 products on a large scale as early as 2010. The safety of clf3 is still controversial due to its active chemical properties. There is no report on the industrialization of clf3 in China. In 2014, China Shipbuilding 718 Institute applied for a patent for the preparation of chlorine trifluoride.

The cleaning effect of high-purity F2 must be much better than that of fluoride. In essence, many fluorocarbons are carriers of fluorine gas, and the real effect is still element fluorine. However, because of the strong activity of fluorine gas, its use is limited, and the on-site fluorine production technology is still under attack.

Conclusion: traditional varieties are gradually controlled independently, and advanced technology and environmental protection gas are gradually catching up

On the whole, the development level of fluorine-containing special gas in China is acceptable. The mainstream cleaning and etching gases such as tetrafluoromethane, hexafluoroethane, nitrogen trifluoride and sulfur hexafluoride have gradually acquired the independent supply capacity, and the products have been supplied to first-line manufacturers such as TSMC and SMIC. However, there is still a big gap with overseas manufacturers in the layout of etch gas for advanced manufacturing process and new environment-friendly fluorine-containing gases such as hexafluorobutadiene and carbonyl fluoride.

Nitrous oxide (N2O, nitrous oxide)

Nitrous oxide gas, commonly known as nitrous oxide, molecular formula N2O. High purity nitrous oxide gas is mainly used in semiconductor, LCD, OLED manufacturing process oxidation, chemical vapor deposition (CVD deposition of silicon nitride nitrogen source) and other processes. With the increasing market demand for semiconductor chips and liquid crystal display panels, the consumption of nitrous oxide as an important gas material will also increase year by year.

High purity nitrous oxide is an important raw material for deposition of SiO2 film, masking film, passive film and antireflection film in PECVD process. The purity of N2O directly affects the purity of SiO2 film. If the impurity content is high, the deposited SiO2 film has many particles, is not bright, and the surface refractive index of the manufacturer is not uniform, it is not conducive to the photolithography process. If the content of trace water in N2O is high, the hydrogen content of SiO2 film will be high, and the density of SiO2 film can not meet the requirements, which will lead to the instability of the device working state and weak anti electromagnetic radiation ability. Therefore, in order to ensure the quality and reliability of optoelectronic devices, the purity of nitrous oxide must be more than 5N.

The main production processes of N2O include the traditional heating decomposition of ammonium nitrate and the purification of tail gas from adipic acid plant. Compared with the dry decomposition of ammonium nitrate, the process of N2O purification by waste gas recovery is not acceptable in some areas, but the cost advantage of N2O purification by waste gas recovery is very prominent. It is understood that there are many enterprises planning to carry out N2O recycling in China, most of which are under construction. It is reported that a certain enterprise in Fuling, Chongqing has reached the capacity of recycling N2O. Once the production capacity of these manufacturers is released, the price of domestic N2O will drop sharply. The long-term stable supply of raw materials from upstream adipic acid tail gas is one of the keys to the purification of nitrous oxide by recovery method. In terms of technology, the technology of removing carbon dioxide from tail gas by various amine solvents is relatively mature. The key of removing light component impurities by distillation is the way of overhead refrigeration cycle and its economy.

In 2017, the domestic N2O market was in short supply and the demand increased sharply, which led to the price soaring. On the supply side, due to the sudden change in the supply and demand of raw material tail gas of a domestic nitrous oxide recycling enterprise, combined with the accident of nitrous oxide plant in the United States and other comprehensive factors, the N2O supply in the market is seriously insufficient; on the demand side, thanks to the rapid development of the domestic liquid crystal industry, the demand of TFT-LCD for N2O increased significantly in 2017. The imbalance between supply and demand eventually led to a sharp rise in N2O prices during the year.

After 2017, due to the gradual breakthrough in product quality of domestic tail gas recovery process, and a certain amount of new production capacity of ammonium nitrate thermal decomposition process, N2O price is expected to enter the downward channel.

silane

In the semiconductor industry, silane is mainly used to make high-purity polysilicon, silicon dioxide thin film by vapor deposition, silicon nitride thin film, polysilicon isolation layer, polysilicon ohmic contact layer, heterogeneous or homogeneous silicon epitaxial growth raw materials, ion implantation source and laser medium, and can also be used to make solar cells, optical fibers and photoelectric sensors.

In the semiconductor production process, silane is the key "source" gas in PECVD and LPCVD film-forming process. In addition to semiconductor applications, silane is also an important raw material in the manufacture of LED and TFT-LCD. China's silane products used to rely heavily on imports. After the localization of Henan Shoushan silane (now silane Technology), the domestic silane supply structure and price have been completely rewritten and balanced. At present, China's domestic silane can fully meet the quality requirements of photovoltaic solar energy, liquid crystal display, led and other fields, but for some chip manufacturing users with higher quality requirements, domestic silane still needs efforts in purification, detection and other aspects. At the same time, with the development trend of larger wafer size and smaller linewidth, the gas quality of source materials should be advanced.

(methylsilane)

Methylsilane, namely silicon tetrahydride, is the largest amount of silane, so methylsilane is often referred to as silane directly. At present, the mainstream production processes of methylsilane include: silicon magnesium alloy process (Komatsu magnesium silicide process), chlorosilane disproportionation process (Union Carbide disproportionation process) and metal hydride process (new silane process invented by MEMC company)

The main domestic manufacturers of electronic grade silane include silane Technology (listed on the new third board), Zhongning silicon industry (a subsidiary of polyfluoro), Tianhong Ruike (a joint venture between Shaanxi nonferrous Tianhong and rec of the United States), Xingyang technology, Zhongneng silicon industry and other manufacturers, which have their own polysilicon production capacity. The main products are mainly used in photovoltaic and other fields.

Through joint research and development with Shanghai Jiaotong University and China chemical saiding Engineering Co., Ltd., silane technology completed the first phase of zsn high purity silane production line with an annual output of 600 tons in September 2014, which was officially put into production in the second half of 2015, with product purity up to 8N, successfully breaking the import monopoly.

Silane

Due to the special chemical characteristics (easy decomposition) of silane, in PECVD and LPCVD manufacturing process, the film forming temperature is much lower than silane, the film forming rate is fast, the film quality is smooth and uniform, and the silicon content in the molecule of silane is much higher than silane. Therefore, there will be a broad application space for silane in the future. At present, many chip factories begin to try to use silicon with a certain concentration Sih4-si2h6 gas mixture. Mitsui East Asia Chemical Co., Ltd., Showa Electric Co., Ltd. and other companies in Japan built a 100 kg silane production line as early as the 1980s, and voltaix Inc. in the United States even owned propylsilane products. Taiwan Specialty Chemical Co., Ltd. also began to recover and purify silane products in 2013, with a large scale of production capacity, and is expected to become one of the world's major suppliers of silane and propylsilane. In 2018, Zhongmei Jing acquired 30.93% of the shares of Taiwan Special Chemical Co., Ltd. for RMB 990 million.

In China, at present, both Beifang Teqi and Huate Co., Ltd. sell silane products, but Huate Co., Ltd. does not have silane production line, so it should be sold by filling with purchased raw gas. Among other manufacturers, Zhejiang Huzhou Xunding semiconductor materials Co., Ltd. has a production capacity of 2000 tons of silane and 240 tons of silane, which will start construction in 2016 and is expected to be put into production in 2019; Quanjiao agtai also has a production capacity of 200 tons of silane and 20 tons of silane, of which 100 tons of silane and 10 tons of silane were announced in October 2018.

In the aspect of scientific research, Professor Yu Jingsong of Zhejiang University has studied silane earlier in China, and has certain attainments in the research of this variety. He has published relevant articles and patents such as "analysis of preparation methods of silane", which should be a reliable technical partner for relevant domestic enterprises.

Phosphorane, arsenane

The properties, preparation methods and functions of phosphine and arsenane in semiconductor industry are similar, and most of the manufacturers are the same, so they are discussed together. Phosphorane and arsenane are very important electron gases in semiconductor process, which are mostly used in ion implantation, doping and other processes. Phosphorane is an important n-type doping source in semiconductor device manufacturing. Meanwhile, phosphorane is also used in polycrystalline silicon chemical vapor deposition, epitaxial gap materials, ion implantation process, MOCVD process, phosphor silicon glass passivation film preparation and other processes. Arsenane is mainly used for n-type doping in epitaxial silicon, n-type diffusion in silicon, ion implantation, growth of gallium arsenide and gallium arsenide phosphate, and formation of semiconductor compounds with IIIA / VA group elements. In addition, AsH3 has very important applications in optoelectronics, solar cells and microwave devices. As an important material in arsenane semiconductor process, there is no substitute so far. For many years, the import of arsenane has been controlled and banned by foreign countries, which poses a threat to China's national security and economic development. Therefore, it is of great significance and urgent to produce high-purity arsenane made in China.

Phosphine and arsenane are highly dangerous, flammable, explosive and highly toxic gases, and their production and use face high safety barriers. Under the background of increasing pressure of domestic safety production, the characteristics of their flammable, explosive and highly toxic also hinder the development of domestic related industries to a certain extent: taking arsenane as an example, it can form a combustible mixture with air, and the fire limit volume fraction is 0 4.5%-64%。 AsH3 is extremely toxic, and the maximum allowable concentration in the air is 0.2 mg / m3, which is especially harmful to human lungs, liver and nervous system.

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(b) borane

Borane is commonly referred to as ethylborane, which is used as a dopant for gaseous impurity source, ion implantation and boron doping oxidation diffusion in semiconductor industry, mainly as a dopant in the production of p-type semiconductor chips. It can also be used as a high energy fuel for rockets and missiles. Voltaix, Inc. (acquired by Air France) is a world leader in alkane gases, including electronic ethylborane. It produces a large amount of ethylborane mixed gases every year and sells them all over the world. Due to the unstable chemical properties of pure ethylborane, it is very difficult to transport from overseas, so the localization of ethylborane is very important. During the "sixth five year plan" period, our country once carried out the research of ethylborane, but it is a pity that great changes have taken place due to the continuous changes of the system. Fortunately, Baoding North Special Gas Co., Ltd. in Hebei Province has realized the mass production of high-purity ethylborane through continuous efforts of technical transformation and upgrading, and they produce high-purity bottled ethylborane It has passed many certification tests at home and abroad, and the use effect is good. North special gas has become the main supply source of diborane for semiconductor in China. It is understood that they will continue to expand the mass production of synthesis and purification equipment on the original basis, so as to make the purity of products to a higher level.

Ethylborane is usually prepared by the reaction of sodium hydride and boron trifluoride in organic solvent. The production process is as follows: the air in the reaction system is pumped out by vacuum pump, the kerosene solution of sodium hydride and ethyl ether solution of boron trifluoride are slowly dropped into the reactor, the sodium fluoride crystal and ethylborane gas are obtained by heating reaction, and the crude product of ethylborane is condensed and purified to obtain high-purity ethylborane gas.

In addition to North special gas, Jingzhou Taihe gas has a capacity of 100 kg of ethane borane. In April 2019, the EIA capacity will be expanded by 3 tons, which is currently in the EIA publicity stage. The raising investment project of Huate shares includes the production capacity of 30000 tons of ethylborane, but it is a warehousing operation project, and Huate itself does not produce ethylborane.

Boron trichloride

High purity boron trichloride is mainly used in chemical vapor deposition (CVD) film forming process and plasma dry etching process in IC manufacturing process, which have high technical requirements and great impact on circuit yield. It will play a key role in the quality of IC products, and can not be replaced by other electronic gases. Its impurity content and purity directly affect the quality, performance, technical index and yield of IC and electronic components. In order to ensure the quality and reliability of IC products, it is required that the purity of boron trichloride must be above 99.999% (5N).

Before 2016, China did not have the production capacity of more than 5N high-purity boron trichloride gas, which was totally imported from several large companies in the United States, Britain, Japan and other countries. Imported products are not only expensive and have a long ordering cycle, but also restricted and restricted by sensitive uses. Therefore, it is urgent to research and develop high-purity boron trichloride above 5N through domestic independent innovation, and form a stable supply capacity in batches, so as to meet the use requirements of old electronic components and new products under research, and fundamentally solve the passive situation of high-purity boron trichloride, a key supporting material, relying on imports and being controlled by others. In the world, only a few foreign gas companies, such as American air products company, American Prax company and British BOC company, have the ability to produce and supply high-purity boron trichloride gas with purity more than 5N.

By the end of 2018, there are at least three companies carrying out boron trichloride purification production in China, and many other companies are in the process of project R & D demonstration. Due to the mature synthesis technology of boron trichloride crude products and the use of highly toxic chemical chlorine in the synthesis, most electronic grade boron trichloride manufacturers adopt the route of purification of purchased crude products, and the manufacturers themselves do not synthesize boron trichloride. In 2019, cryogenic energy and Hubei Jingzhou Taihe Gas Co., Ltd., listed on the new third board, respectively launched 200 tons and 150 tons of electronic boron trichloride production capacity.

Boron trifluoride

High purity boron trifluoride is a p-type doping source for epitaxy, diffusion and ion implantation of silicon and germanium. It can also be used as a plasma etching gas. High purity BF3 is used as boron dopant in silicon ion implantation. The chip has the characteristics of high integration, high density, smaller volume and better performance.

The research on boron trifluoride in China started in the late 1950s. Guangming research and Design Institute of chemical industry has carried out the research on the synthesis, analysis and complexation of boron trifluoride for the production of high-energy fuel borane (NAH + BF3 → B2H6 + NaF). The basic research and New Technology Bureau of the State Science and Technology Commission has signed research and development contracts for ultra pure gases and alkanes with Guangming research and Design Institute of chemical industry, Beijing oxygen plant, Zhejiang University and Baoding Hongxing monocrystalline silicon plant respectively. The gas varieties include SiH4, PH3, B2H6, AsH3, BF3, NH3, HCl and other "sixth five year" projects.

It is worth noting that modern IC production lines have new requirements for boron trifluoride: the abundance value of isotope 11b in boron trifluoride should reach a certain value. It is well known that isotope separation technology is difficult. There are still many technologies in this field in China, and there is no industrialization in this field at present.

At present, only Fujian Bochun materials and Guangming Institute of Haohua science and technology have electronic grade boron trifluoride capacity in China. Bochun materials has 0.5 tons of boron trifluoride capacity in the ultra precision electronic mixed gas project filed in December 2015; Haohua science and technology's raising investment project includes 1 ton of capacity, and Guangming Institute has also carried out relevant pilot projects before. The project invested by Huate shares also has a production capacity of 10 tons of boron trifluoride, but it is a storage and distribution project and does not engage in production itself; the situation of NANDA optoelectronics is similar to that of Huate shares. Dayang Rizhao of Japan has 240 tons of electronic chemical production capacity in Yangzhou Chemical Industry Park, including boron trifluoride products. The project was approved by EIA in April 2017. On the whole, there is a big gap between Chinese boron trifluoride manufacturers and overseas manufacturers, electronic grade has not yet formed a large-scale production capacity, and there is still a distance from industrialization in 11b isotope separation, and they may still rely on overseas supply in a short time.

Germane

In semiconductor process, as the precursor of CVD Si Ge film, germane is mainly used to manufacture electronic devices, such as integrated circuits, optoelectronic devices, especially heterojunction diode transistors. In the heterojunction diode transistor (HBT), the thin SiGe layer is grown on the silicon wafer as the substrate of the HBT. Compared with the traditional HBT, the SiGe HBT has obvious advantages in speed, response frequency and gain, and its speed and frequency response can be compared with the more expensive GA as HBT. In addition, germane is also an important precursor gas for solar cells.

The synthesis methods of germane are mainly divided into chemical reduction method and electrolysis method. ① Chemical reduction method is usually used to reduce germanide by simple and complex metal hydride. Generally, germanium magnesium alloy, germanium dioxide and germanium tetrachloride can be used as germanium containing reagents, and lithium hydride, potassium hydride, lithium borohydride, sodium borohydride, lithium aluminum hydride and diisobutyl alumina can be used as reducing agents. The reduction reaction can be carried out in aqueous solution, inorganic solvent and organic solvent, or in molten state or solid state

Decomposition of germanium magnesium alloy by hydrochloric acid: gemg2 + 4hcl → geh4 + 2mgcl2

Reduction of germanium tetrachloride by lithium aluminum hydride: LiAlH4 + GeCl4 → geh4 + LiCl + AlCl3

Reduction of germanium tetrachloride by sodium borohydride: GeCl4 + NaBH4 + 3naoh → geh4 + B (OH) 3 + 4nacl

② In electrolysis, germanium is usually used as cathode and molybdenum or cadmium as cathode. During the reaction, methylgermane and hydrogen are produced at the cathode, and molybdenum or cadmium oxides are produced at the anode. It can also electrolyze the acidic or alkaline solution of germanium dioxide to prepare germanane from the alkaline solution, and finally get germanane, germanium and hydrogen. The material conversion efficiency is more than 80%.

It is worth noting that the production, storage and transportation of germane are highly dangerous, which objectively creates a high technical barrier to the germane industry: germane has a strong autocatalytic property. Once it is decomposed to form a metal covering film, it will decompose rapidly, so its decomposition explosion risk is very high. Germane explosion accidents have occurred in both nipponate and Takashi germane factories in Japan.

Before 2016, China's high-purity germane was basically completely dependent on imports. At that time, more than 90% of the global germane market was monopolized by voltaix (which has been acquired by Air France), and the import price was as high as tens of millions of RMB per ton, which was often hindered by the tension and changes of the international situation. In 2016, Bochun materials, located in Yongchun County, Quanzhou, Fujian Province, broke the import monopoly of germane. At present, its high-purity germane production capacity is said to have reached the first in the world. In the field of thin-film solar energy, its product market share is very high, and it has obtained very high market returns. On August 15, 2017, Fujian Bochun joined hands with American semiconductor material manufacturer and distributor entergres Inc. to establish a joint venture in Quanzhou, Fujian Province, aiming at China's high-end semiconductor market. As early as 2016, Bochun OEM entergres Inc. it is understood that entergres Inc has a monopoly patent product SDS in chip manufacturing process. From OEM to the present substantial cooperative production, in the current good market background, the cooperation of the company is undoubtedly promising, and the competitiveness of its products is worthy of attention.

At present, the domestic companies that have or plan to have germane production capacity mainly include Bochun gas, Huate Co., Ltd., Taihe gas and central equipment Co., Ltd. Qiyuan takes the lead, among which Bochun gas is the domestic leader. Huate shares has 10 tons of germane production capacity in the raised investment project, and has relevant technical reserves before. The public information shows that patents and germane related papers have been published. Since 2012, the production capacity of germanium, arsenic and titane in Qizhou has not been in the lead.

Hydrogen selenide

Hydrogen selenide is an important raw material and reducing gas for the production of semiconductor materials. It can form p-n structure protection layer and isolation layer on the surface of semiconductor, and can also be used as doping gas. In addition, high purity hydrogen selenide has very important applications in the fields of national defense and aerospace.

At present, there are two main methods to prepare hydrogen selenide. One is to prepare hydrogen selenide by the decomposition reaction of metal selenide and water. The second method is obtained by direct combination of high purity hydrogen and selenium at 250-570 ℃.

Before 2010, China's hydrogen selenide products were completely dependent on foreign imports, and only the United States Air chemical products (AP & C) could be produced in the world. In 2010, the annual sales volume of the products was US $500 million, and the supply was in short supply, and China was banned. In 2010, Taihe gas medical and optoelectronic special gas project in Jingzhou, Hubei Province was put into operation, which broke the import monopoly of hydrogen selenide in China. At present, the production capacity of Taihe gas hydrogen selenide is 3 tons. Huate shares has 40 tons of hydrogen selenide production capacity in the projects listed on the science and technology innovation board; the R & D and production base project of Guangming Institute of Haohua technology includes 20 tons of hydrogen selenide production capacity.

Cos

Carbonyl sulfur is widely used in the etching field of circuit micronization in recent years, and its etching effect in dry etching is very obvious, which attracts much attention. Japanese companies such as Kanto chemical and dayangri acid were put on the market in 2011. Dayangri acid carried out purification and filling of COS in Kawasaki. Industrial grade cos bottled raw materials are available in Japan, which provides convenient conditions for cos purification.

COS is usually synthesized by the reaction of elemental sulfur and CO: S + CO → cos. The dry synthesis of carbonyl sulfur is very similar to that of hydrogen sulfide and hydrogen selenide, but there are some differences: the synthesis of COS needs FeS2, Na2S, NIS, CaSO4 and other sulfur-containing metal compounds as catalysts. High purity cos can be obtained by adsorption and distillation.

At present, only Jingzhou Taihe gas is used to carry out the industrial synthesis of carbonyl sulfur in China. In the 653 ton special gas project announced in July 2019, it has a capacity of 70 tons of carbonyl sulfur.

The localization of semiconductors to build a special gas race track, industry integration, the general trend of increasing the securitization rate

With the improvement of chip localization rate, the localization of key electronic special gas is the trend of the times. However, the localization of chips is bound to be accompanied by a sharp drop in the price of related products, and there will be corresponding pressure on the price reduction of electronic special gas at the end of raw materials. Therefore, the improvement of the quality of domestic special gas does not mean the rise of product price. On the contrary, due to the acceleration of the catch-up process of the domestic semiconductor industry, the technological progress pressure of the semiconductor material track will be greater than before. Only the enterprises with strong R & D strength and perfect product pipeline layout can withstand the pressure of technological process iteration and maintain their position in the track.

In addition, the domestic electronic special gas production capacity is relatively scattered, there are a large number of leading companies in the subdivision field, the proportion of asset securitization is low, and most high-quality targets are not listed. Therefore, the follow-up integration of the industry and the improvement of the securitization rate will be the general trend.

Development of domestic electronic special gas standards

Main board listed companies

Huate Co., Ltd.: fluorocarbon production capacity is large, and lithography gas has passed ASML certification

The company's main industrial gas production, especially the production of electronic special gas. In the aspect of electronic special gas, the company is good at fluorocarbon gas, and the production capacity of high-purity hexafluoroethane is large. According to the company's prospectus, the company is the first gas company in China to break the import restrictions of high-purity hexafluoroethane, high-purity trifluoromethane, high-purity octafluoropropane, high-purity carbon dioxide, high-purity carbon monoxide, high-purity nitric oxide, AR / F / NE mixture, Kr / NE mixture, AR / NE mixture, Kr / F / NE mixture and other products.

According to the company's prospectus, its customers cover well-known customers in IC, panel and other industries at home and abroad, and its photoresist gas has passed ASML certification.

According to the disclosure of the prospectus, the investment direction of the company's raised capital in this technology innovation board listing includes four parts: ① gas center construction and warehousing operation project; ② electronic gas production and purification and industrial gas filling project; ③ intelligent operation project; ④ supplement of working capital. Among them, ① (hereinafter referred to as gas center project) and ② (hereinafter referred to as production purification project) are production projects.

The company was established in 1999 with a registered capital of 3 million yuan. In July 2015, the company was established as a joint stock limited company. On February 22, 2017, the company's shares were listed on the new third board. On April 16, 2018, the company's shares were terminated in the national small and medium-sized enterprise share transfer system. On April 12, 2019, the company's shares were listed on the new third board The company issued a prospectus for its initial public offering and listing on the science and technology innovation board.

In 2018, the company achieved revenue of 820 million yuan, a year-on-year increase of 3.9%, and net profit of 68 million yuan, a year-on-year increase of 40%. From 2014 to 2018, the company's operating revenue CAGR is about 6%, and the net profit attributable to the parent CAGR is about 7%.

In terms of gross profit rate and net profit rate, according to the company's prospectus, the company's products are mostly priced by the cost plus method. Therefore, in recent years, the company's gross profit rate and net profit rate fluctuate little, of which the gross profit rate is basically stable in the range of 30-40%. The main reason for the decline in 18 years is that the company's new product nitrous oxide and new overseas customers have lowered the gross profit rate. In terms of expense rate, the company's sales expense rate is at 15%, which is determined by the nature of the industry: the company needs a careful transportation plan to deliver industrial gas products to customers, so the company bears a considerable amount of transportation and miscellaneous expenses; the company's management expense rate is about 6%, of which R & D investment accounts for 20% of the operating income About 3%, the company's explanation is that considering its own capital situation, the company focuses on some directions with great technical difficulties but less R & D investment in the early stage to make breakthroughs. At the same time, the company's R & D investment is concentrated in the special gas sector. If the revenue of special gas sector replaces the total revenue, the company's R & D expense rate is about 5%; in terms of financial expense rate, the company maintains a long-term stability With a low asset liability ratio of 25% and almost no long-term debt, there is almost no financial expense.

Special gas business contributed mainly to revenue and gross profit. Special gases contribute about 50% of the company's revenue contract and 60% of its gross profit; ordinary industrial gases (mainly oxygen, nitrogen, industrial ammonia, etc.) business has been running smoothly in recent years, with a relatively stable scale, contributing about 30% of the company's revenue and 20% of its gross profit, which is a supplement to the company's performance at a relatively small stage. In addition, the equipment and engineering section is the gas storage equipment, gas supply system and related services that the company sells when providing gas products to customers, and can also contribute to certain achievements.

Haohua Technology: started from the R & D platform of "two bombs and one satellite", leading domestic high purity sulfur hexafluoride

Previously, the company was Tianyi technology, mainly engaged in PSA gas separation technology and complete sets of devices, catalyst products, carbon chemistry and engineering design. At the end of 2018, China Haohua injected 11 chemical research institutes into the listed companies and renamed Haohua technology. In the whole year of 2018 and the first half of 2019, the company achieved revenue of 4.18 billion yuan and 2.28 billion yuan respectively, with a year-on-year increase of 15% and 18% respectively; and realized net profit of 525 million yuan and 257 million yuan respectively, with a year-on-year increase of 61% and 6% respectively.

Due to the large number of subordinate research institutes, the company has a wide business segment. In addition to the original PSA and related projects and catalysts of Tianyi technology, it also includes electronic gas, fluorine materials, polyurethane, chemical propellants, coatings and other businesses. In the 2018 annual report, the company's electronic gas business accounted for 7% of revenue, 8% of gross profit and 34% of gross profit. According to the disclosure statement of China Daily News in 2019, electronic gas, polyurethane and chemical propellants will be disclosed together, accounting for 25% of the total revenue and 29% of the gross profit.

The company's special gas products are mainly located in Liming hospital and Guangming hospital. Liming Institute, formerly a scientific research institute directly under the former Ministry of chemical industry, is a comprehensive research and development organization with chemical propellant and raw material development as its main business for the mission of "two bombs and one satellite". Liming Institute started the research and development of high-purity sulfur hexafluoride in 2002. In 2006, the production capacity reached 3000 tons. Industrial grade products are mainly used for electronic equipment insulation. Around 2006, with the vigorous development of the basic power industry by the state, liming Institute rapidly occupied the market. Using high purity SF6 products instead of NF3 in CVD cleaning process can effectively reduce the cost. The company's products have reached 5N level in 2006 and gradually passed the customer certification. At present, they have reached 5n5 level, which is the leader of high purity sulfur hexafluoride in China. In terms of nitrogen trifluoride, the company and Korea Dacheng joint venture construction production line, phase I of 1000 tons started in March 2015, reached production in July 2016, and phase II of 1000 tons has been put into operation in October 2018.

The predecessor of Guangming institute can be traced back to Dalian Institute of chemical industry, Ministry of chemical industry. After many changes in the management system of state-owned chemical research institutes, Guangming Institute was transformed into an enterprise owned by the whole people and renamed Guangming research and Design Institute of chemical industry. Guangming Institute has carried out the research on the synthesis, analysis and complexation of boron trifluoride for the production of high energy fuel ethane (NAH + BF3 → B2H6 + NaF). The basic research and New Technology Bureau of the State Science and Technology Commission has signed research and development contracts for ultra pure gases and alkanes with Guangming research and Design Institute of chemical industry, Beijing oxygen plant, Zhejiang University and Baoding Hongxing monocrystalline silicon plant respectively. The gas varieties include SiH4, PH3, B2H6, AsH3, BF3, NH3, HCl and other "sixth five year" projects. By July 2010, the source from Guangming Chemical Industry Institute said that its self-developed ultra pure ammonia products and supporting technologies have been widely used in aerospace, photovoltaic and solar fields.

At present, liming Institute's special gas products are mainly nitrogen trifluoride and sulfur hexafluoride, with the production capacity of 2000 tons and 2800 tons respectively; Guangming Institute has invested in the construction of special gas R & D and production base project in Dalian, with the products including 1000 tons of ultra pure ammonia, 40 tons of green nitrogen tetroxide, 200 tons of hydrogen sulfide, 20 tons of hydrogen selenide, 1 ton of boron trifluoride, 3 tons of phosphine, borane and arsenane, and 50 tons of high-purity chlorine It is expected to be put into production in 2019.

Juhua Co., Ltd. (zhongjuxin): an old fluorine chemical leader in the electronic special gas business, advanced process etching gas has the first mover advantage

In April 2018, Juhua transferred 100% of the shares of Borui electronics and Kaisheng fluorochemical to zhongjuxin, making the above two subsidiaries listed (zhongjuxin big fund and Juhua share each holding shares) 39%）。

The company's special gas business is mainly concentrated in Borui electronics and Borui China nitrate, a joint venture subsidiary of Borui electronics and Japan Central nitrate. The annual output of 1000 tons of high-purity hydrogen chloride, 500 tons of high-purity chlorine gas and 1000 tons of pharmaceutical grade hydrogen chloride of Borui electronics phase I project is 154 million yuan, which has been put into operation. The expansion project of 500 tons of high-purity chlorine gas and 500 tons of high-purity hydrogen chloride has also been announced in October 2018. In the second phase, the annual output of 200 tons of high-purity carbon dioxide, 150 tons of nitrous oxide, 500 tons of fluorine-containing gas, 200 tons of chlorine containing gas and 4000 bottles of electronic gas mixture is RMB 120 million, and RMB 320000 has been invested by the end of 2017.

In February 2019, the company's environmental impact assessment announced that the production capacity of fluorine-containing series of electronic special gas projects includes 250 tons of trifluoromethane, 180 tons of octafluorocyclobutane, 5 tons of monofluoromethane, 17 tons of difluoromethane, 3 tons of pentafluoroethane, 55 tons of hexafluoroethane, 5 tons of octafluoropropane and 5 tons of octafluorocyclopentene. After the project is completed, the estimated revenue is 50.35 million yuan and the profit and tax is 12.82 million yuan. The company has the first mover advantage in etching gas layout of octafluorocyclobutane, hexafluorobutadiene, octafluorocyclopentene and other advanced processes.

Nanda optoelectronics: the leader of phosphane and arsenane in China, and plans to purchase NF3 and SF6

The company is mainly engaged in Mo source and electronic special gas business. In the half year report of 2019, the special gas business accounts for 33% of revenue, 44% of gross profit and 61% of gross profit, which is the business sector with the highest gross profit margin. In the semi annual report of 2019, the company realized a revenue of 139 million yuan, a year-on-year increase of 10%; realized a net profit of 26 million yuan, a year-on-year decrease of 9%.

The company's existing special gas business mainly includes phosphine and arsenane. In April 2014, the company used the over raised capital of 65 million yuan to increase the capital of Quanjiao NANDA optoelectronics, a wholly-owned subsidiary, and implemented the project of "R & D and pilot test of high-purity arsenane, phosphine and other special gas". Then, in 2015, Quanjiao NANDA optoelectronics increased its capital and shares. At present, arsenane and phosphane have been successfully mass produced and supplied to many customers. In 2018, the company's high-purity phosphine production capacity is about 35 tons and arsenane production capacity is 15 tons. According to the record of investor relations activities in early 2019, the average utilization rate of phosphine and arsenane production capacity of the company was about 80% in 2018. The company has started the project of expanding the production capacity of electronic special gas, and is expected to double the production capacity by the end of 2019. In January 2019, the company's phosphane and arsenane expansion project was approved by the EIA. The first phase project will expand the production of 17.5 tons of phosphane, and the second phase project will expand the production of 17.5 tons of phosphane + 15 tons of arsenane.

In August 2019, the company announced that it plans to acquire 57.97% equity of Shandong feiyuan Gas Co., Ltd. by means of cash acquisition and capital increase. Feiyuan gas has a capacity of 1000 tons of NF3 and 2000 tons of SF6. From the beginning of 2018 and the beginning of 2019 to July 11, feiyuan gas achieved revenue of 108 million yuan and 82 million yuan respectively, with net profit of - 20 million yuan and - 10 million yuan. As of July 11, the company had net assets of 12 million yuan, asset liability ratio of 95%, and the appraisal price of all equity of feiyuan gas was 216 million yuan.

Focus on SF6 and CF4

The traditional business of Yake technology is flame retardant business. From 2016 to 2017, the company acquired Huafei electronics, Jiangsu Xianke and Chengdu kemete successively to enter the electronic materials business. At present, the electronic materials business is mainly divided into three parts: IC precursor, electronic special gas and spherical silicon powder for packaging. In 2019, the electronic special gas business of Zhongbao accounts for 20% of the company's revenue and 28% of its gross profit. In recent years, the company's performance has maintained rapid growth. In 2019, Zhongbao achieved a revenue of 861 million yuan, a year-on-year increase of 33%, and realized a net profit of 100 million yuan, a year-on-year increase of 81%.

KOMET's special gas layout is mainly fluorine-containing gas, with the production capacity of carbon tetrachloride and Sulfur Hexafluoride as domestic leaders. At present, it has the production capacity of 1200 tons and 7000 tons respectively, and there are still 3500 tons of nitrogen trifluoride projects under construction.

KEMET gas: the leader of tail gas air separation industry

The company is formerly a three-stage unit of Sinopec, which is a food grade liquid carbon dioxide production enterprise with large annual production capacity based on chemical tail gas in China. Other production capacity includes argon, hydrogen and rectifying gas

In September 2017, the company announced the special gas project, with a total investment of 310million yuan, and 25 new production units for electronic special gas projects, adopting low-temperature adsorption, deep cold distillation separation, electrolysis and catalytic synthesis technology. According to the company's environmental assessment information, electronic special gas projects have been announced, with a total investment of RMB 197million, including 712 tons of carbon dioxide, 31 tons of carbon monoxide, 180 tons of nitrogen, 25 tons of helium, 257 tons of argon, 13 tons of hydrogen, 44 tons of krypton, 5.3 tons of xenon, 85 tons of neon, 3000 bottles of fluorine-based laser mixture, 1800 dynamic mixed gas, 600 hydrogen chloride based laser mixture gas Bottle, expected to be put into operation in 2021.

New third board listed company

Silane Technology: silane leader, pioneer breaking import monopoly

Founded in May 2012, the company is a subordinate enterprise of pingcoal Shenma Group. It is the pioneer of breaking import monopoly in domestic silane field. Through joint research and development with Shanghai Jiaotong University and China chemical saiding engineering company, the company has built a phase I high purity silane production line with annual output of 600 tons zsn method in September 2014, and transferred to formal production in the second half of 2015, with the product purity up to 8N Level, successfully breaking the import monopoly.

At the end of 2018, the company has a capacity of 3000 tons of silane and 1500 tons of electronic polysilicon (1800 tons of silane for self use). After the project reaches the full production stage, it will occupy 40% domestic silane, 15% of electronic polysilicon and more than 10% of silane market share in other regions of Asia, with an annual output value of RMB 1billion and profit and tax of RMB 200 million. In 2019, China Daily achieved a revenue of 210million yuan, an increase of 221% year-on-year; net profit attributable to parent company reached 9.41 million yuan, an increase of 374% year-on-year. The company will further build 10000 ton high-purity silane, polysilicon and other projects in the future, and will also enter the domestic capital market, with the goal of building a double billion enterprises with output value and market value.

In the next five years, the company plans to expand the construction scale of silane and develop and produce electronic grade polysilicon in two phases, with a total investment of 6 billion yuan. Among them: the second phase project is expected to invest 1 billion yuan to build an annual 3000 ton high-purity silane gas and supporting 1500 ton electronic grade (partial melting grade) polysilicon project. The third phase of the project will invest 5 billion yuan to build 15000 tons of high-purity silane gas, 10000 tons of electronic grade polysilicon and 1000 tons of zone melting grade polysilicon. After the third phase project is completed and put into operation, the output value of silane will reach 10 billion yuan and the total profit and tax will reach 2 billion yuan.

Jinhong gas: the leader of ultra pure ammonia, the pioneer of breaking import monopoly

The company's business is divided into three parts: special gas, industrial gas and clean energy. The main products of special gas are ultra pure ammonia and hydrogen. The purity of ultra pure ammonia reaches 7n, which is the first in China. It has successfully broken the import monopoly. Other special gas products include helium, nitrous oxide, chlorine, hydrogen chloride and high purity Carbon dioxide, hexafluoroethane, high purity octafluorocyclobutane, sulfur hexafluoride, ultra pure nitrogen, high purity oxygen, ultra high purity mixture, medical oxygen, etc.

In the first half of 2019, the company realized a revenue of 546 million yuan, an increase of 8% over the same period of last year, and a net profit of 75 million yuan, an increase of 17% over the same period of last year. In 2019, the company's special gas business accounts for 40% of its revenue, 46% of its gross profit and 55% of its gross profit, making it the sector with the highest gross profit margin.

The company landed on the new third board in 2014 and submitted the gem application materials in 2016. Recently, the company withdrew the gem application materials on August 2, 2019, and began to receive listing guidance again on August 23.

The company's major customers are relatively scattered, and most of the top five customers are domestic chip and optical fiber and cable manufacturers.

Six construction projects are disclosed in the company's prospectus, two of which involve special gas, including "high purity gas and high purity mixed gas filling project for VLSI" and "high purity hydrogen and multi-function special gas project"

Outstanding unlisted target

Perrault gas (718 research institutes): R & D driven special gas leader, NF3 and wf6 break the import monopoly and strive for the top position in the world

Founded in 1966, the 718th Research Institute of China Shipbuilding Industry Corporation is a state-level scientific research institution integrating scientific research and development, design and production, and technical services. Its headquarters is located in Handan City, Hebei Province, and its branch is located in Beichen District, Tianjin city, covering an area of about 900000 square meters. It is mainly engaged in the professional research and design of high energy chemistry, three prevention technology, hydrogen production and hydrogen energy development, special gas, fine chemical industry, petroleum logging, environmental engineering, gas analysis, automatic control, nuclear power hydrogen elimination, frequency conversion energy saving, air purification, medical oxygen production, etc.

718 Institute began the research on nitrogen trifluoride in the 1980s. With the support of major national projects, after years of civil military integration and continuous technological innovation, it has successively developed high-purity nitrogen trifluoride, tungsten hexafluoride and other special gas series products, breaking the monopoly of foreign enterprises for more than ten years and ending the project In the era of high price of related products in the field, the market price of the main product nitrogen trifluoride has dropped sharply, which has changed the unfavorable situation of China's long-term dependence on imports of high-purity special gas.

Perrett gas is a subsidiary of 718 special gas companies. It was founded at the end of 2016. Its main products in electronic special gas are nitrogen trifluoride and tungsten hexafluoride. In addition, in the fields of traditional and advanced fluorocarbon gases such as hexafluoroethane, octafluoropropane, octafluorocyclobutane, hexafluorobutadiene and other fluorine-containing and chlorine-containing special gases such as Silicon tetrafluoride, hydrogen chloride, hydrogen fluoride and other products, as well as isotope gas deuterium gas and other fields have layout.

At present, the production capacity of nitrogen trifluoride and tungsten hexafluoride in 718 institutes are 6000 tons and 800 tons respectively, and the production scale ranks first in China. The domestic market coverage of nitrogen trifluoride and tungsten hexafluoride is more than 95%, and the international market coverage is 50%. The other seven gases and 10 mixed gases have been successfully developed and have batch production conditions, and have been tested and certified by domestic semiconductor leading enterprises. The company's 5400 ton new material project passed the EIA acceptance in October 2018, adding 3000 tons of nitrogen trifluoride, 500 tons of tungsten hexafluoride and 5 tons of high purity deuterium gas; the company has another 7300 ton new material and 80000 ton liquid nitrogen project, which is planned to be put into operation in June 2020, including 4500 tons of nitrogen trifluoride, 1500 tons of tungsten hexafluoride, 200 tons of hexafluorobutadiene and 60 tons of silicon tetrafluoride At that time, the company is expected to become the world's largest supplier of nitrogen trifluoride and tungsten hexafluoride.

Bochun materials: germane leading, break import monopoly, lay out high-end special gas, and look forward to the future

Founded in 2009, Fujian Bochun materials has the world's largest germane production base in Quanzhou, Fujian Province, and a gas R & D center in Kingman, Arizona, USA. Mr. Chen Guofu, chairman of the company, is a Bachelor of chemistry from the University of California, Berkeley, MBA from the University of Southern California, and a member of the semiconductor gas Committee. He has more than 18 years of experience in semiconductor gas manufacturing, quality management, and market operation. He has worked for Scott special gas, Matheson, Dayang acid and other international well-known gas companies in the United States, 2016 He was selected as the fifth batch of talents of "100 talents plan" in Fujian Province.

Before 2016, China's high-purity germane was basically completely dependent on imports. At that time, more than 90% of the global germane market was monopolized by voltaix (which has been acquired by Air France), and the import price was as high as tens of millions of RMB per ton, which was often hindered by the tension and changes of the international situation. In 2016, Bochun materials, located in Yongchun County, Quanzhou, Fujian Province, broke the import monopoly of germane. At present, its high-purity germane production capacity is said to have reached the first in the world. In the field of thin-film solar energy, its product market share is very high, and it has obtained very high market returns. On August 15, 2017, Fujian Bochun joined hands with American semiconductor material manufacturer and distributor entergres to set up a joint venture in Quanzhou, Fujian Province, aiming at China's high-end semiconductor market. As early as 2016, Bochun OEM entergres products. Entergres has a monopoly patent in the negative pressure cylinder SDS products, which is introduced in detail in the previous chapters of this paper.

In addition to the traditional germane products, the company has a layout in high-end special gases, such as isotope gas deuterium gas, silane, boron trifluoride, phosphine, arsenane, borane, carbonyl sulfur, rare gas and other products.

Lvling gas: pioneer of nitrous oxide tail gas recovery method, electronic grade silicon tetrafluoride to achieve batch supply

Nitrous oxide (N2O) is commonly known as nitrous oxide. High purity nitrous oxide is mainly used in semiconductor, LCD, OLED manufacturing process oxidation, chemical vapor deposition and other processes. The traditional nitrous oxide production process uses ammonium nitrate heating decomposition method, the equipment investment is large, there are certain safety and environmental protection risks, and the purchase of raw materials, transportation and storage also need complex procedures. On the one hand, the adipic acid tail gas recovery process independently developed by Lvling gas makes use of the tail gas of adipic acid plant, which is low-cost and environmentally friendly. On the other hand, it avoids the potential safety hazard of ammonium nitrate explosion in traditional nitrous oxide production. The first phase of 6000 tons production capacity of the company was put into production in August 2014, and the product purity reached 6N. The second phase of 6000 tons was expected to be put into production in 2017, but it is speculated that it should have been put into production.

In July 2017, the company put into production 300 tons of HFC, HFC, HFC and other products in Tianjin. High purity electronic grade silicon tetrafluoride products have passed the test of SMIC international, China Resources Shanghua and other domestic well-known companies, and have achieved batch supply. At present, high purity electronic grade silicon tetrafluoride products have been exported to semiconductor customers in large quantities, such as the United States and Japan.

Taihe gas: the pioneer of high purity chlorine in China, with broad prospects for high-end special gas projects

Founded in 2010, the company focuses on the R & D and production of electronic special gas products, taking the lead in independent R & D and production of high-purity chlorine, hydrogen chloride, ethylborane and other special gas products for semiconductor industry in China; the company's high-purity chlorine has won the support of national strong base engineering; and the "production technology of 1000 tons of high-purity chlorine per year" has obtained the scientific and technological achievement certification of Hubei Provincial Science and technology department. The company's products fill the domestic production gap, gradually replace imports, and export to South Korea, Taiwan, Japan and other overseas markets; Taihe with stable quality, stable supply to win customer trust, is a number of domestic and foreign well-known enterprises qualified suppliers.

The company's trimethylboron, germane, hydrogen selenide, ethylborane and other products have been put into production in 2010 EIA announcement; in May 2016, the company announced 2500 tons of special gas project, with the production capacity of 1000 tons / year high-purity chlorine and 1200 tons / year high-purity hydrogen chloride, which have also been put into production; in July 2019, the company announced 653 tons of special gas project, with the production capacity of 3 tons of ethylborane and 100 tons of hydrogen sulfide They are all high-end special gas products with large demand for import substitution, such as 300 tons of boron trichloride, 150 tons of boron trichloride, 30 tons of fluorine gas, 70 tons of carbonyl sulfur, 30 tons of boron trifluoride, 200 tons of propylene and 10 tons of penta (dimethylamino) tantalum.

Other outstanding non listed targets

There are a large number of unlisted special gas standards, which will not be introduced one by one. Other unlisted special gas standards, such as domestic substitution pioneer of borane, North special gas, electronic grade phosphorus chemical leader Witton crystal phosphorus, silane leader Huzhou Xunding, comprehensive distribution of special gas products, EPEC and cryogenic energy, are excellent unlisted standards in China.