CN102992286B - Preparation method of high-purity zinc phosphide - Google Patents
Preparation method of high-purity zinc phosphide Download PDFInfo
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- CN102992286B CN102992286B CN201210502875.2A CN201210502875A CN102992286B CN 102992286 B CN102992286 B CN 102992286B CN 201210502875 A CN201210502875 A CN 201210502875A CN 102992286 B CN102992286 B CN 102992286B
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Abstract
The invention discloses a preparation method of high-purity zinc phosphide, which comprises the following steps of: 1) quartz tube pretreatment; 2) dosing; 3) tube sealing; 4) high-temperature synthesis; and 5) product treatment. According to the invention, high-purity phosphorus and high-purity zinc are directly combined to produce high-purity zinc phosphide, the main reaction process is carried out after the temperature reaches the melting point of zinc, the reaction is actually a steam reaction, and the method is an element direct synthesis method; the requirements for the form of raw materials are not very strict; the raw material is not processed, and the requirement for high purity is met; the pressure in a tube is controlled through temperature control operations such as slow heating, constant temperature, slow cooling and the like; the phosphorus steam pressure in the quartz tube is successfully controlled through length allocation of a heating area and a condensation area for synthesizing a quartz tube, and safe synthesis of a large amount of zinc phosphide is realized; and relatively high yield of a product is realized by controlling the length of the condensation area and the heating area, and the product is applied to the application fields of photoelectric device manufacturing, diffusion sources, nano materials and the like.
Description
Technical field
The present invention relates to a kind of preparation method of high-purity zinc phosphide.
Background technology
High-purity zinc phosphide is a kind of II-V family semiconductor material, energy gap 1.5ev.Zinc phosphide material is shown great attention to by people just in recent years, and the compound semiconductors such as while gallium arsenide, indium phosphide are semiconductor materials indispensable in Modern wireless communication, optical communication field.And in the device technologies such as indium phosphide, often adopt highly purified zinc phosphide as diffuse source.Zinc phosphide is one of current various countries semiconductor material of just actively dropping into applied research, be included in the applied research on solar cell, one-dimensional nano-device, therefore along with the continuous expansion of its Application Areas, to the demand of zinc phosphide material, also will roll up, development prospect is optimistic.
Prior art has two kinds of technical schemes: a kind of is combustion method, and another kind is ZnP
2vacuum Heat decomposition method, the shortcoming that described two schemes mainly exists: 1. pair raw material form is had relatively high expectations.2. not exclusively, synthetic ratio is lower in reaction.3. comparison in equipment is complicated, and cost of investment is high.4. product does not reach high-purity requirement.
Summary of the invention
The technical problem to be solved in the present invention is: for combustion method, ZnP
2the defect that yield rate is low, cost of investment is high, product does not reach high-purity requirement of Vacuum Heat decomposition method, design a set of can scale production the preparation method of high-purity zinc phosphide of high-purity zinc phosphide.
The object of the invention realizes by following technical proposals:
1, a preparation method for high-purity zinc phosphide, comprises the steps:
1) silica tube pre-treatment: clean silica tube, before charging, at silica tube inwall precoating layer carbon film;
Avoid material at high temperature to react with silica tube.
2) batching: take zinc and phosphorus, the zinc taking and the mol ratio of phosphorus are 3:2, and the zinc weighing up and phosphorus are packed in silica tube;
3) tube sealing: making in silica tube is vacuum, and the reaction zone in silica tube is sealed;
4) high temperature is synthetic: silica tube is put into synthetic furnace, and synthesize according to following heating schedule, concrete heating schedule is as follows:
Under normal temperature, heat and within 5-10 minute, reach 210 ℃, through within 20-30 minute, being heated to 410 ℃ and constant temperature 20-30 minute, through within 30-40 minute, being heated to 600 ℃ and constant temperature 20-30 minute, through within 30-60 minute, being heated to 1050 ℃ and constant temperature 8-10 hour, blowing out.
5) product treatment: break silica tube and take out zinc phosphide product, put into drying receptacle sealing and preserve.
2,, as optimal way, described high temperature is synthetic is further:
4) high temperature is synthetic: silica tube is put into synthetic furnace, and synthesize according to following heating schedule, concrete heating schedule is as follows:
Under normal temperature, heat and within 7 minutes, reach 210 ℃, through within 25 minutes, being heated to 410 ℃ and constant temperature 25 minutes, through within 35 minutes, being heated to 600 ℃ and constant temperature 25 minutes, through within 45 minutes, being heated to 1050 ℃ and constant temperature 9 hours, blowing out.
3, as optimal way, the method for precoating carbon film is to carry acetone steam to enter the silica tube under high temperature constant temperature with high-purity argon gas bubbling, and acetone cracking makes silica tube coat carbon film.
4,, as optimal way, described high temperature is 900-1100 ℃.
5, as optimal way, described clean silica tube is for first cleaning with buck, and high purity water rushes to neutral, then soaks 24 hours with chloroazotic acid, then extremely neutral with high purity water punching.
With buck, clean for wipe oil, with chloroazotic acid, soak 24 hours to remove impurity metal ion.
6, as optimal way, the method for described tube sealing is: after charging, with the sealing of quartzy envelope bubble, after silica tube is evacuated to vacuum, with oxyhydrogen flame, by silica tube inwall and envelope bubble outer wall sintering, realize the sealing to reaction zone.
7,, as optimal way, the described vacuum tightness that is evacuated to vacuum is 5 * 10
-4pa-10 * 10
-4pa.
8,, as optimal way, envelope bubble is apart from quartzy mouth of pipe 10cm, the condensing zone length 25cm outside heating zone.
9,, as optimal way, maximum charging capacity during batching in silica tube is 500g.
10, as optimal way, the phosphorus taking in batching is the red phosphorus of purity 6N, and zinc is the zinc of purity 6N.
The following describes the basis of design of each step:
In zinc phosphide building-up process, the problem of prevent exploding is the topmost technical barrier that will solve.The key that solves this technical barrier is the control to vapour pressure, reflection be exactly the control to temperature in practice, for this reason autonomous design synthetic furnace and heating schedule.Silica tube is positioned in the horizontal chamber oven of one section of temperature control and synthesizes, heating schedule arrange like this according to being: avoid the excessive generation blasted pipe phenomenon of high purity phosphorus vapour pressure in production process, improve synthetic ratio, ensure the yield rate of product, if temperature is too short lower than above-mentioned scope, time simultaneously, can cause yield rate low.
Envelope bubble be take interior position as reaction zone, and reaction zone is divided into two regions: condensing zone, heating zone, when high temperature synthesizes, the length of heating zone and condensing zone distributes the control of phosphorous vapor pressure is had to very vital role.Phosphorus steam, through being gaseous state in heating zone, is converted into liquid state in condensing zone, and phosphorus steam experience again to a working cycle of gaseous state, can be avoided the excessive booster that prevents of pressure from gaseous state to liquid state, and therefore condenser zone length setting being set is 25cm.
Be heated to 1050 ℃ and constant temperature 8-10 hour, object is to guarantee to react completely, and makes product meet stoichiometric ratio requirement.
Because the cracking of acetone is more than 800 degree, silica tube material is limited the highlyest bears 1100 ℃ and softening, so the temperature setting of precoating carbon film is set to 900-1100 ℃.
Oxygen can affect quality product, so silica tube is evacuated to vacuum tightness, is 5 * 10
-4pa-10 * 10
-4pa, also helps by low this scope that is reduced to of initial vapour pressure the possibility that prevents later reaction bombing.
The present invention uses the high purity phosphorus (being that purity is 99.9999%) of 6N and the high purity zinc (being that purity is 99.9999%) of 6N directly to change and produces high-purity zinc phosphide (99.9999%), after main reaction process occurs in the fusing point that temperature reaches zinc, the actual reaction belonging between steam, belong to element direct synthesis technique, advantage comprises: to the form of raw material, require not bery strict, raw material does not pass through processing treatment, meets high-purity requirement; The present invention operates control tube internal pressure by temperature controls such as slow intensification, constant temperature, slow coolings, and to synthetic silica tube heating region, condenser zone length allocation, successfully controls phosphorous vapor in silica tube and press, and the safety that realizes relatively large zinc phosphide is synthetic; By the control of condenser zone and hot zone length, realize product compared with high rate of finished products.Product is made for photoelectric device, diffuse source, the Application Areass such as nano material.
Accompanying drawing explanation
Fig. 1 is the apparatus structure schematic diagram of precoating carbon film.
Fig. 2 is the apparatus structure schematic diagram of tube sealing.
Wherein, 1 for envelope bubble, 2 be raw material, 3 for silica tube, 4 for vacuum pump, 5 for vacuum adapter, 6 for deoxidation stove, 7 for ventpipe, 8 for bubbling bottle, 9 be acetone.
The device of precoating carbon film comprises that silica tube 3, ventpipe 7, the ventpipe 7 in the middle of silica tube 3 of deoxidation stove 6, deoxidation stove 6 inside are communicated to bubbling bottle 8, bubbling bottle 8 is inner is acetone 9, outside argon gas passes into acetone, makes acetone steam by ventpipe 7, enter to the inside of silica tube 3.
The device of tube sealing comprises vacuum pump 4, and vacuum pump 4 is communicated to silica tube 3 by vacuum adapter 5, steeps 1 raw material 2 is enclosed in silica tube in the middle of silica tube 3 by envelope.
Embodiment
Following non-limiting examples is used for illustrating the present invention.
embodiment 1
1, a preparation method for high-purity zinc phosphide, comprises the steps:
1) silica tube pre-treatment:
Clean silica tube, first cleans with buck, and high purity water rushes to neutral, then soaks 24 hours with chloroazotic acid, then extremely neutral with high purity water punching, before charging, at silica tube inwall precoating layer carbon film; The method of precoating carbon film is to carry acetone steam to enter 900 ℃ of silica tubes under constant temperature with high-purity argon gas bubbling, and acetone cracking makes silica tube coat carbon film.The length of silica tube is 60cm, and diameter is 40mm, and thickness of pipe is 3mm.
2) batching:
21) raw material is prepared: the red phosphorus piece of the purity 6N of picking diameter 5-7mm is put into ground glass stoppered bottle, and to the argon gas that is filled with purity 5N in bottle as protection gas; The fritter of the zinc of purity 6N being made to 10g left and right, deoxidation treatment is done on surface, is placed on anti-oxidation in argon atmosphere;
Deoxidation refers to and utilizes vacuum system, gets rid of the oxygen in raw material, and silica tube prevents from boning under raw material oxidation high temperature.
22) take zinc and phosphorus, the zinc taking and the mol ratio of phosphorus are 3:2, and the zinc weighing up and phosphorus are packed in silica tube; Maximum charging capacity during batching in silica tube is 500g.
3) tube sealing: with the sealing of quartzy envelope bubble, silica tube is vacuumized after charging, making vacuum tightness is 5 * 10
-4paPa, by silica tube inwall and envelope bubble outer wall sintering, realizes the sealing to reaction zone with oxyhydrogen flame, and envelope bubble is apart from quartzy mouth of pipe 10cm, the condensing zone length 25cm outside heating zone.
4) high temperature is synthetic: silica tube is put into synthetic furnace, and synthesize according to following heating schedule, concrete heating schedule is as follows:
Under normal temperature, heat and within 5 minutes, reach 210 ℃, through within 20 minutes, being heated to 410 ℃ and constant temperature 20 minutes, through within 30 minutes, being heated to 600 ℃ and constant temperature 20 minutes, through within 30 minutes, being heated to 1050 ℃ and constant temperature 8 hours, blowing out.
5) product treatment:
Break silica tube and take out zinc phosphide product, put into dry Plastic Bottle sealing and preserve.Because zinc phosphide is highly toxic substance, solid waste need be put into special collection box.
embodiment 2
1, a preparation method for high-purity zinc phosphide, comprises the steps:
1) silica tube pre-treatment:
Clean silica tube, first cleans with buck, and high purity water rushes to neutral, then soaks 24 hours with chloroazotic acid, then extremely neutral with high purity water punching, before charging, at silica tube inwall precoating layer carbon film; The method of precoating carbon film is to carry acetone steam to enter 1100 ℃ of silica tubes under constant temperature with high-purity argon gas bubbling, and acetone cracking makes silica tube coat carbon film.The length of silica tube is 60cm, and diameter is 40mm, and thickness of pipe is 3mm.
2) batching:
21) raw material is prepared: the red phosphorus piece of the purity 6N of picking diameter 8-10mm is put into ground glass stoppered bottle, and to the argon gas that is filled with purity 5N in bottle as protection gas; The fritter of the zinc of purity 6N being made to 20g left and right, deoxidation treatment is done on surface, is placed on anti-oxidation in argon atmosphere;
Deoxidation refers to and utilizes vacuum system, gets rid of the oxygen in raw material, and silica tube prevents from boning under raw material oxidation high temperature.
22) take zinc and phosphorus, the zinc taking and the mol ratio of phosphorus are 3:2, and the zinc weighing up and phosphorus are packed in silica tube; Maximum charging capacity during batching in silica tube is 500g.
3) tube sealing: with the sealing of quartzy envelope bubble, silica tube is vacuumized after charging, making vacuum tightness is 10 * 10
-4pa, by silica tube inwall and envelope bubble outer wall sintering, realizes the sealing to reaction zone with oxyhydrogen flame, and envelope bubble is apart from quartzy mouth of pipe 10cm, the condensing zone length 25cm outside heating zone.
4) high temperature is synthetic: silica tube is put into synthetic furnace, and synthesize according to following heating schedule, concrete heating schedule is as follows:
Under normal temperature, heat and within 10 minutes, reach 210 ℃, through within 30 minutes, being heated to 410 ℃ and constant temperature 30 minutes, through within 40 minutes, being heated to 600 ℃ and constant temperature 30 minutes, through within 60 minutes, being heated to 1050 ℃ and constant temperature 10 hours, blowing out.
5) product treatment:
Break silica tube and take out zinc phosphide product, put into dry Plastic Bottle sealing and preserve.Because zinc phosphide is highly toxic substance, solid waste need be put into special collection box.
embodiment 3
1, a preparation method for high-purity zinc phosphide, comprises the steps:
1) silica tube pre-treatment:
Clean silica tube, first cleans with buck, and high purity water rushes to neutral, then soaks 24 hours with chloroazotic acid, then extremely neutral with high purity water punching, before charging, at silica tube inwall precoating layer carbon film; The method of precoating carbon film is to carry acetone steam to enter 1000 ℃ of silica tubes under constant temperature with high-purity argon gas bubbling, and acetone cracking makes silica tube coat carbon film.The length of silica tube is 60cm, and diameter is 40mm, and thickness of pipe is 3mm.
2) batching:
21) raw material is prepared: picking diameter is not more than the red phosphorus piece of the purity 6N of 7mm and puts into ground glass stoppered bottle, and to the argon gas that is filled with purity 5N in bottle as protection gas; The fritter of the zinc of purity 6N being made to 15g left and right, deoxidation treatment is done on surface, is placed on anti-oxidation in argon atmosphere;
Deoxidation refers to and utilizes vacuum system, gets rid of the oxygen in raw material, and silica tube prevents from boning under raw material oxidation high temperature.
22) take zinc and phosphorus, the zinc taking and the mol ratio of phosphorus are 3:2, and the zinc weighing up and phosphorus are packed in silica tube; Maximum charging capacity during batching in silica tube is 500g.
3) tube sealing: with the sealing of quartzy envelope bubble, silica tube is vacuumized after charging, making vacuum tightness is 7 * 10
-4pa, by silica tube inwall and envelope bubble outer wall sintering, realizes the sealing to reaction zone with oxyhydrogen flame, and envelope bubble is apart from quartzy mouth of pipe 10cm, the condensing zone length 25cm outside heating zone.
4) high temperature is synthetic: silica tube is put into synthetic furnace, and synthesize according to following heating schedule, concrete heating schedule is as follows:
Under normal temperature, heat and within 8 minutes, reach 210 ℃, through within 25 minutes, being heated to 410 ℃ and constant temperature 25 minutes, through within 35 minutes, being heated to 600 ℃ and constant temperature 25 minutes, through within 45 minutes, being heated to 1050 ℃ and constant temperature 9 hours, blowing out.
5) product treatment:
Break silica tube and take out zinc phosphide product, put into dry Plastic Bottle sealing and preserve.Because zinc phosphide is highly toxic substance, solid waste need be put into special collection box.
embodiment 4
1, a preparation method for high-purity zinc phosphide, comprises the steps:
1) silica tube pre-treatment:
Clean silica tube, first cleans with buck, and high purity water rushes to neutral, then soaks 24 hours with chloroazotic acid, then extremely neutral with high purity water punching, before charging, at silica tube inwall precoating layer carbon film; The method of precoating carbon film is to carry acetone steam to enter 950 ℃ of silica tubes under constant temperature with high-purity argon gas bubbling, and acetone cracking makes silica tube coat carbon film.The length of silica tube is 60cm, and diameter is 40mm, and thickness of pipe is 3mm.
2) batching:
21) raw material is prepared: the red phosphorus piece of the purity 6N of picking diameter 6-9mm is put into ground glass stoppered bottle, and to the argon gas that is filled with purity 5N in bottle as protection gas; The fritter of the zinc of purity 6N being made to 12-18g left and right, deoxidation treatment is done on surface, is placed on anti-oxidation in argon atmosphere;
Deoxidation refers to and utilizes vacuum system, gets rid of the oxygen in raw material, and silica tube prevents from boning under raw material oxidation high temperature.
22) take zinc and phosphorus, the zinc taking and the mol ratio of phosphorus are 3:2, and the zinc weighing up and phosphorus are packed in silica tube; Maximum charging capacity during batching in silica tube is 500g.
3) tube sealing: with the sealing of quartzy envelope bubble, silica tube is vacuumized after charging, making vacuum tightness is 6 * 10
-4pa, by silica tube inwall and envelope bubble outer wall sintering, realizes the sealing to reaction zone with oxyhydrogen flame, and envelope bubble is apart from quartzy mouth of pipe 10cm, the condensing zone length 25cm outside heating zone.
4) high temperature is synthetic: silica tube is put into synthetic furnace, and synthesize according to following heating schedule, concrete heating schedule is as follows:
Under normal temperature, heat and within 7 minutes, reach 210 ℃, through within 25 minutes, being heated to 410 ℃ and constant temperature 25 minutes, through within 35 minutes, being heated to 600 ℃ and constant temperature 25 minutes, through within 45 minutes, being heated to 1050 ℃ and constant temperature 9 hours, blowing out.
5) product treatment:
Break silica tube and take out zinc phosphide product, put into dry Plastic Bottle sealing and preserve.Because zinc phosphide is highly toxic substance, solid waste need be put into special collection box.
embodiment 5
1, a preparation method for high-purity zinc phosphide, comprises the steps:
1) silica tube pre-treatment:
Clean silica tube, first cleans with buck, and high purity water rushes to neutral, then soaks 24 hours with chloroazotic acid, then extremely neutral with high purity water punching, before charging, at silica tube inwall precoating layer carbon film; The method of precoating carbon film is to carry acetone steam to enter the 920-1080 ℃ of silica tube under constant temperature with high-purity argon gas bubbling, and acetone cracking makes silica tube coat carbon film.The length of silica tube is 60cm, and diameter is 40mm, and thickness of pipe is 3mm.
2) batching:
21) raw material is prepared: the red phosphorus piece of the purity 6N of picking diameter 7-8mm is put into ground glass stoppered bottle, and to the argon gas that is filled with purity 5N in bottle as protection gas; The fritter of the zinc of purity 6N being made to 14-18g left and right, deoxidation treatment is done on surface, is placed on anti-oxidation in argon atmosphere;
Deoxidation refers to and utilizes vacuum system, gets rid of the oxygen in raw material, and silica tube prevents from boning under raw material oxidation high temperature.
22) take zinc and phosphorus, the zinc taking and the mol ratio of phosphorus are 3:2, and the zinc weighing up and phosphorus are packed in silica tube; Maximum charging capacity during batching in silica tube is 500g.
3) tube sealing: with the sealing of quartzy envelope bubble, silica tube is vacuumized after charging, making vacuum tightness is 6 * 10
-4pa-9 * 10
-4pa, by silica tube inwall and envelope bubble outer wall sintering, realizes the sealing to reaction zone with oxyhydrogen flame, and envelope bubble is apart from quartzy mouth of pipe 10cm, the condensing zone length 25cm outside heating zone.
4) high temperature is synthetic: silica tube is put into synthetic furnace, and synthesize according to following heating schedule, concrete heating schedule is as follows:
Under normal temperature, heat and within 6-9 minute, reach 210 ℃, through within 22-28 minute, being heated to 410 ℃ and constant temperature 22-26 minute, through within 32-38 minute, being heated to 600 ℃ and constant temperature 22-28 minute, through within 35-55 minute, being heated to 1050 ℃ and constant temperature 8.5-9.5 hour, blowing out.
5) product treatment:
Break silica tube and take out zinc phosphide product, put into dry Plastic Bottle sealing and preserve.Because zinc phosphide is highly toxic substance, solid waste need be put into special collection box.
Claims (8)
1. a preparation method for high-purity zinc phosphide, is characterized in that comprising the steps:
1) silica tube pre-treatment: clean silica tube, before charging, at silica tube inwall precoating layer carbon film, the method for precoating carbon film is to carry acetone steam to enter the 900-1100 ℃ of silica tube under constant temperature with high-purity argon gas bubbling, acetone cracking makes silica tube coat carbon film;
2) batching: take zinc and phosphorus, the zinc taking and the mol ratio of phosphorus are 3:2, and the zinc weighing up and phosphorus are packed in silica tube;
3) tube sealing: making in silica tube is vacuum, and the reaction zone in silica tube is sealed;
4) high temperature is synthetic: silica tube is put into synthetic furnace, and synthesize according to following heating schedule, concrete heating schedule is as follows:
Under normal temperature, heat and within 5-10 minute, reach 210 ℃, through within 20-30 minute, being heated to 410 ℃ and constant temperature 20-30 minute, through within 30-40 minute, being heated to 600 ℃ and constant temperature 20-30 minute, through within 30-60 minute, being heated to 1050 ℃ and constant temperature 8-10 hour, blowing out;
5) product treatment: break silica tube and take out zinc phosphide product, put into drying receptacle sealing and preserve.
2. preparation method as claimed in claim 1, is characterized in that: described high temperature is synthetic is further:
4) high temperature is synthetic: silica tube is put into synthetic furnace, and synthesize according to following heating schedule, concrete heating schedule is as follows:
Under normal temperature, heat and within 7 minutes, reach 210 ℃, through within 25 minutes, being heated to 410 ℃ and constant temperature 25 minutes, through within 35 minutes, being heated to 600 ℃ and constant temperature 25 minutes, through within 45 minutes, being heated to 1050 ℃ and constant temperature 9 hours, blowing out.
3. preparation method as claimed in claim 1, is characterized in that: described clean silica tube is for first cleaning with buck, and high purity water rushes to neutral, then soaks 24 hours with chloroazotic acid, then extremely neutral with high purity water punching.
4. preparation method as claimed in claim 1, is characterized in that: the method for described tube sealing is: after charging, with the sealing of quartzy envelope bubble, after silica tube is evacuated to vacuum, with oxyhydrogen flame, by silica tube inwall and envelope bubble outer wall sintering, realize the sealing to reaction zone.
5. preparation method as claimed in claim 4, is characterized in that: the described vacuum tightness that is evacuated to vacuum is 5 * 10
-4pa-10 * 10
-4pa.
6. preparation method as claimed in claim 4, is characterized in that: envelope bubble is apart from quartzy mouth of pipe 10cm, the condensing zone length 25cm outside heating zone.
7. the preparation method as described in claim 1 or 2 or 4 or 5, is characterized in that: maximum charging capacity during batching in silica tube is 500g.
8. preparation method as claimed in claim 7, is characterized in that: the phosphorus taking in batching is the red phosphorus of purity 6N, and zinc is the zinc of purity 6N.
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| CN103950909A (en) * | 2014-04-25 | 2014-07-30 | 云南锡业集团有限责任公司研究设计院 | Preparation method of zinc phosphide |
| CN106477540A (en) * | 2015-11-25 | 2017-03-08 | 衡阳恒荣高纯半导体材料有限公司 | A kind of preparation method of high-purity zinc phosphide |
| CN106495113B (en) * | 2016-10-08 | 2018-07-03 | 广东先导稀材股份有限公司 | The preparation method of high-purity zinc phosphide |
| CN110093623B (en) * | 2019-04-30 | 2020-10-27 | 苏州科技大学 | Phosphated stainless steel material, and preparation method and application thereof |
| CN112680781B (en) * | 2020-12-09 | 2023-10-03 | 清远先导材料有限公司 | Cadmium telluride crystal growth device and growth method thereof |
| CN115477322A (en) * | 2022-09-29 | 2022-12-16 | 云南驰宏国际锗业有限公司 | Ultra-high purity GeCl 4 Preparation method |
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| CN101734630A (en) * | 2009-12-30 | 2010-06-16 | 峨嵋半导体材料研究所 | Method for preparing high-purity cadmium telluride |
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| CN101734630A (en) * | 2009-12-30 | 2010-06-16 | 峨嵋半导体材料研究所 | Method for preparing high-purity cadmium telluride |
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