JPS6140755B2 - - Google Patents
Info
- Publication number
- JPS6140755B2 JPS6140755B2 JP3822279A JP3822279A JPS6140755B2 JP S6140755 B2 JPS6140755 B2 JP S6140755B2 JP 3822279 A JP3822279 A JP 3822279A JP 3822279 A JP3822279 A JP 3822279A JP S6140755 B2 JPS6140755 B2 JP S6140755B2
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- selenium
- selenide
- vapor
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 32
- PFNQVRZLDWYSCW-UHFFFAOYSA-N (fluoren-9-ylideneamino) n-naphthalen-1-ylcarbamate Chemical compound C12=CC=CC=C2C2=CC=CC=C2C1=NOC(=O)NC1=CC=CC2=CC=CC=C12 PFNQVRZLDWYSCW-UHFFFAOYSA-N 0.000 claims description 25
- 239000011701 zinc Substances 0.000 claims description 25
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 23
- 239000011669 selenium Substances 0.000 claims description 23
- 229910052725 zinc Inorganic materials 0.000 claims description 23
- 229910052711 selenium Inorganic materials 0.000 claims description 21
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 20
- 229910052786 argon Inorganic materials 0.000 description 10
- 239000012159 carrier gas Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 229910000058 selane Inorganic materials 0.000 description 10
- 239000002994 raw material Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- XYUNNDAEUQFHGV-UHFFFAOYSA-N [Se].[Se] Chemical compound [Se].[Se] XYUNNDAEUQFHGV-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Chemical Vapour Deposition (AREA)
Description
【発明の詳細な説明】
本発明は、良質のセレン化亜鉛（ZnSe）を安
価に製造することができるセレン化亜鉛の製造方
法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing zinc selenide (ZnSe) that can produce high quality zinc selenide (ZnSe) at low cost.
近年、赤外線を利用する機器の発達に伴い、赤
外線に対して透明な材料の需要が急増している。
セレン化亜鉛は、これらの材料の中でも機械的強
度、耐湿性、光学的性質等の点で優れた特性を兼
ね備えた有望な材料であり、特に炭酸ガスレーザ
の大出力化の成否を握る鍵であるとされている半
透明鏡への適用を目指して、活発な開発が進めら
れている。しかし、セレン化亜鉛は、製造に際し
て高価な原料を使用しなければならないため、製
造コストが極めて高くなるという問題がある。 In recent years, with the development of equipment that utilizes infrared rays, the demand for materials that are transparent to infrared rays has rapidly increased.
Among these materials, zinc selenide is a promising material that has excellent properties in terms of mechanical strength, moisture resistance, optical properties, etc., and is the key to the success or failure of increasing the output power of carbon dioxide lasers. Active development is underway with the aim of applying it to semi-transparent mirrors. However, zinc selenide has a problem in that it requires the use of expensive raw materials during production, resulting in extremely high production costs.
本発明は、上述した従来の問題点に鑑みてなさ
れたものであるが、まず、本発明の理解を容易に
するため、従来用いられてきたCVD（Chemichal
Vapour Deposition）法によるセレン化亜鉛の製
造方法について説明する。 The present invention has been made in view of the above-mentioned conventional problems.Firstly, in order to facilitate understanding of the present invention, the conventional CVD (Chemical
The method for manufacturing zinc selenide using the Vapor Deposition method will be explained.
第１図は、セレン化亜鉛の従来の製造方法に使
用する製造装置の概念図であり、１０はセレン化
水素（H2Se）１を充填した原料ガス容器、２０
はキヤリアガス２を充填したキヤリアガス容器、
３０は亜鉛蒸気生成装置、４０は反応装置、５０
はコールド・トラツプである。不活性のキヤリア
ガスとして、通常、アルゴンを使用し、また、原
料ガスのセレン化水素も、通常はアルゴン等のキ
ヤリアガスで希釈して使用する。亜鉛蒸気生成装
置３０は、亜鉛蒸気生成室３１と、その中に収容
された溶融亜鉛浴３２と、ヒータ３３とから構成
されており、溶融亜鉛浴３２中には高純度の金属
亜鉛３が収容される。反応装置４０は、反応室４
１とヒータ４２とから構成されており、反応室４
１内には基板６０が収容される。上述した装置を
用いて、原料ガス容器１０内のセレン化水素と、
亜鉛蒸気生成装置３０内で生成された亜鉛蒸気と
をキヤリアガスのアルゴンにより反応室４１内に
送り込んで混合すると、
Zn（Ｖ）＋H2Se（Ｖ）→ZnSe（Ｓ）＋H2（ｇ）
………(1)
なる反応が生じ、基板６０上にセレン化亜鉛の堆
積層６が形成される。反応装置の後段において、
毒性の強い未反応セレン化水素をコールド・トラ
ツプ５０により回収し、残余のガスをポンプで排
気する。 FIG. 1 is a conceptual diagram of the production equipment used in the conventional production method of zinc selenide, in which 10 is a raw material gas container filled with hydrogen selenide (H 2 Se) 1, 20
is a carrier gas container filled with carrier gas 2,
30 is a zinc vapor generation device, 40 is a reaction device, 50
is a cold trap. Argon is usually used as an inert carrier gas, and hydrogen selenide, which is a raw material gas, is also usually diluted with a carrier gas such as argon. The zinc vapor generating device 30 is composed of a zinc vapor generating chamber 31, a molten zinc bath 32 housed therein, and a heater 33. High purity metal zinc 3 is housed in the molten zinc bath 32. be done. The reaction device 40 has a reaction chamber 4
1 and a heater 42.
A substrate 60 is housed in the inside. Using the above-mentioned device, hydrogen selenide in the raw material gas container 10,
When the zinc vapor generated in the zinc vapor generator 30 is sent into the reaction chamber 41 using argon as a carrier gas and mixed, Zn (V) + H 2 Se (V) → ZnSe (S) + H 2 (g)... ...(1) A reaction occurs, and a deposited layer 6 of zinc selenide is formed on the substrate 60. In the latter stage of the reactor,
Highly toxic unreacted hydrogen selenide is recovered by a cold trap 50, and the remaining gas is exhausted by a pump.
このようなCVD法により相当の品質のセレン
化亜鉛を製造することができるが、その原料とし
て高価なセレン化水素を使用しているので、当然
に製造原価が高くなるという欠点がある。また、
セレン化水素は比較的不安点なガスであり、貯蔵
が長期にわたるとセレンの析出、組成のムラ等の
変質を生じ易く、このため、製造されたセレン化
亜鉛の品質がばらつくおそれがある。さらに、セ
レン化水素は毒性が強いため、高圧充填容器から
の洩れなどに関して安全管理に十分な注意を払わ
なければならないという欠点もある。 Although zinc selenide of considerable quality can be produced by such a CVD method, since expensive hydrogen selenide is used as a raw material, the production cost naturally increases. Also,
Hydrogen selenide is a relatively unstable gas, and when stored for a long period of time, it tends to undergo alterations such as selenium precipitation and compositional unevenness, which may cause variations in the quality of produced zinc selenide. Furthermore, since hydrogen selenide is highly toxic, it also has the disadvantage that sufficient attention must be paid to safety management to prevent leakage from high-pressure filling containers.
本発明は、上述した従来の製造方法の欠点に鑑
みてなされたものであり、その目的とするところ
は、高価なセレン化水素を使用することなく、良
質のセレン化亜鉛を安価に製造することができる
セレン化亜鉛の新規な製造方法を提供することに
ある。 The present invention was made in view of the drawbacks of the conventional production methods described above, and its purpose is to produce high-quality zinc selenide at low cost without using expensive hydrogen selenide. The purpose of the present invention is to provide a new method for producing zinc selenide.
上述した目的を達成する本発明によれば、亜鉛
とセレン（セレニウム）の両者を、化合物として
ではなく単体の蒸気の形態で混合することにより
亜鉛とセレンの直接の反応を生じさせる。 According to the invention, which achieves the above object, a direct reaction between zinc and selenium occurs by mixing both zinc and selenium (selenium) in the form of simple vapors rather than as a compound.
本発明の一実施例によれば、キヤリアガスの異
る流路中に置いた溶融浴から亜鉛蒸気とセレン蒸
気を発生させ、両者の蒸気をキヤリアガスによつ
て反応室内に輸送して混合し、両者の蒸気の間に
直接の反応を生じさせる。 According to one embodiment of the present invention, zinc vapor and selenium vapor are generated from molten baths placed in different flow paths of a carrier gas, and both vapors are transported into a reaction chamber by the carrier gas and mixed. produces a direct reaction between the vapors of the
すなわち、本発明者らは前述の反応式(1)とは全
く異る
Zn（Ｖ）＋Se（Ｖ）→ZnSe（Ｓ） ………(2)
の反応に基くセレン化亜鉛層の堆積が基板上に実
際に生じ、しかも、このような反応が反応速度、
反応生成物の品質等の点で工業的に十分な利用価
値を有していることを実証することによつて、は
じめて、高価な原料の使用を不要とした安価なセ
レン化亜鉛の製造方法に到達したのである。以
下、本発明の更に詳細を実施例によつて説明す
る。 That is, the present inventors discovered that the deposition of a zinc selenide layer based on the reaction of Zn (V) + Se (V) → ZnSe (S) (2), which is completely different from the reaction formula (1) described above, The above reaction actually occurs, and the reaction rate is
By demonstrating that the reaction product has sufficient industrial utility value in terms of quality, etc., we will be able to develop an inexpensive method for producing zinc selenide that does not require the use of expensive raw materials. It has been reached. Hereinafter, further details of the present invention will be explained with reference to Examples.
第２図は、本発明の製造方法の一実施例に使用
する製造装置の概念図であり、本図において第１
図と同一の参照符号を付した要素は、第１図に関
して説明した要素と同一のものである。参照符号
７０で示すセレン蒸気生成装置は、セレン蒸気生
成室７１と、その中に収容された溶融セレン浴７
２と、ヒータ７３とから構成されており、溶融セ
レン浴７２中には高純度の金属セレン５が収容さ
れる。本実施例においては、蒸気生成室３１，７
１、反応室４１、溶融浴３２，７２の全てに石英
を使用し、不活性のキヤリアガスとしてアルゴン
ガスを使用し、基板６０として黒鉛を使用する。 FIG. 2 is a conceptual diagram of a manufacturing apparatus used in an embodiment of the manufacturing method of the present invention.
Elements with the same reference numerals as in the figures are the same as those described with respect to FIG. The selenium vapor generation device designated by reference numeral 70 includes a selenium vapor generation chamber 71 and a molten selenium bath 7 accommodated therein.
2 and a heater 73, and high-purity metal selenium 5 is accommodated in the molten selenium bath 72. In this embodiment, the steam generation chambers 31, 7
1. The reaction chamber 41 and the melt baths 32 and 72 are all made of quartz, argon gas is used as an inert carrier gas, and graphite is used as the substrate 60.
まず、反応装置４０の下流側に設置した排気ポ
ンプ（油回転ポンプ、メカニカル・ブースタその
他水流ポンプなど適宜なものでよい。）を動作さ
せて、亜鉛蒸気生成室３１、セレン蒸気生成室７
１及び反応室４１の各室内を排気する。次に高圧
のアルゴンを充填したキヤリアガス容器２０の減
圧弁を操作して低圧のアルゴンガスを0.02〜２リ
ツトル／分の流量で流出させ、各室内の雰囲気を
10〜100Torr程度の圧力のアルゴンガスで置換す
る。引続き、ヒータ３３，７３及び４２の電源を
投入して、溶融亜鉛浴３２の温度が450℃〜850
℃、溶融セレン浴７２の温度が400℃〜650℃、黒
鉛基板６０の温度が500℃〜850℃の範囲で一定値
となるように各ヒータの発熱量を調整する。 First, the exhaust pump (an oil rotary pump, mechanical booster, or other suitable water pump) installed downstream of the reaction device 40 is operated, and the zinc vapor generation chamber 31 and the selenium vapor generation chamber 7 are operated.
1 and the reaction chamber 41 are evacuated. Next, the pressure reducing valve of the carrier gas container 20 filled with high-pressure argon is operated to flow out low-pressure argon gas at a flow rate of 0.02 to 2 liters/minute, thereby changing the atmosphere in each room.
Replace with argon gas at a pressure of about 10 to 100 Torr. Subsequently, the heaters 33, 73, and 42 are turned on, and the temperature of the molten zinc bath 32 is 450°C to 850°C.
The amount of heat generated by each heater is adjusted so that the temperature of the molten selenium bath 72 is constant in the range of 400°C to 650°C, and the temperature of the graphite substrate 60 is constant in the range of 500°C to 850°C.
このようにすると、加熱された溶融亜鉛浴３２
から亜鉛蒸気が発生し、加熱された溶融セレン浴
からセレン蒸気が発生し、各々の金属蒸気はアル
ゴン気流中を輸送されて反応室４１に達する。両
金属蒸気は反応室４１で混合され、前述した(2)式
の反応によつて生じたセレン化亜鉛が黒鉛基板６
０上に堆積層６を形成する。 In this way, the heated molten zinc bath 32
Zinc vapor is generated from the heated molten selenium bath, selenium vapor is generated from the heated molten selenium bath, and each metal vapor is transported in an argon stream to reach the reaction chamber 41. Both metal vapors are mixed in the reaction chamber 41, and the zinc selenide produced by the reaction of equation (2) described above is applied to the graphite substrate 6.
A deposited layer 6 is formed on 0.
亜鉛蒸気生成室及びセレン蒸気生成室内のアル
ゴン流量をいずれも0.5リツトル／分、溶融亜鉛
浴温度を550℃、溶融セレン浴温度を500℃、黒鉛
基板温度を800℃、反応室内の全ガス圧力を
50Torrとした場合、セレン化亜鉛層６１の堆積
速度は75ミクロン／時であつた。 The argon flow rate in the zinc vapor generation chamber and the selenium vapor generation chamber was both 0.5 liters/min, the molten zinc bath temperature was 550℃, the molten selenium bath temperature was 500℃, the graphite substrate temperature was 800℃, and the total gas pressure in the reaction chamber was
At 50 Torr, the deposition rate of the zinc selenide layer 61 was 75 microns/hour.
亜鉛蒸気生成室及びセレン蒸気生成室内のアル
ゴン流量をいずれも0.75リツトル／分、溶融亜鉛
浴温度を550℃、溶融セレン浴温度を500℃、黒鉛
基板温度を700℃、圧応室内の全ガス圧力を
100Torrとした場合、セレン化亜鉛層６１の堆積
速度は120ミクロン／時であつた。 The argon flow rate in the zinc vapor generation chamber and the selenium vapor generation chamber is both 0.75 liters/min, the molten zinc bath temperature is 550℃, the molten selenium bath temperature is 500℃, the graphite substrate temperature is 700℃, and the total gas pressure in the pressure reaction chamber. of
At 100 Torr, the deposition rate of the zinc selenide layer 61 was 120 microns/hour.
このようにして製造されたセレン化亜鉛の堆積
層は概ね多結晶層の様相を呈し、光学的な評価の
結果、前述した従来方法によつて製造されたもの
と同程度以上の品質を有することが確認された。
なお、堆積層形成後の熱処理条件によつては、更
に品質が向上することも期待される。 The deposited layer of zinc selenide produced in this manner generally has the appearance of a polycrystalline layer, and as a result of optical evaluation, it has been found to have a quality comparable to or better than that produced by the conventional method described above. was confirmed.
Furthermore, it is expected that the quality will further improve depending on the heat treatment conditions after forming the deposited layer.
以上詳細に説明したように、本発明の製造方法
は、亜鉛蒸気とセレン蒸気を直接反応させること
によつて基板上にセレン化亜鉛を堆積させるもの
であるから、高価なセレン化水素を原料として使
用することなく、高品質のセレン化水素を安価に
製造することができる。 As explained in detail above, since the manufacturing method of the present invention deposits zinc selenide on a substrate by directly reacting zinc vapor and selenium vapor, expensive hydrogen selenide is not used as a raw material. High quality hydrogen selenide can be produced at low cost without using it.
第１図は、従来の製造方法に使用する製造装置
の概念図、第２図は、本発明の一実施例に使用す
る製造装置の概念図である。
１……セレン化水素、２……キヤリアガス、３
……金属亜鉛、５……金属セレン、６……セレン
化亜鉛の堆積層、３０……亜鉛蒸気生成装置、４
０……反応装置、５０……コールド・トラツプ、
６０……基板、７０……セレン蒸気生成装置。
FIG. 1 is a conceptual diagram of a manufacturing apparatus used in a conventional manufacturing method, and FIG. 2 is a conceptual diagram of a manufacturing apparatus used in an embodiment of the present invention. 1...Hydrogen selenide, 2...Carrier gas, 3
...Metallic zinc, 5...Metal selenium, 6...Zinc selenide deposited layer, 30...Zinc vapor generator, 4
0...Reactor, 50...Cold trap,
60...Substrate, 70...Selenium vapor generation device.
Claims (1)
成する段階と、両者の蒸気を混合して基板上にセ
レン化亜鉛を堆積する段階とを含むことを特徴と
するセレン化亜鉛の製造方法。1. A method for producing zinc selenide, comprising the steps of generating zinc vapor, generating selenium vapor, and mixing both vapors to deposit zinc selenide on a substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3822279A JPS55130805A (en) | 1979-03-30 | 1979-03-30 | Manufacture of zinc selenide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3822279A JPS55130805A (en) | 1979-03-30 | 1979-03-30 | Manufacture of zinc selenide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS55130805A JPS55130805A (en) | 1980-10-11 |
| JPS6140755B2 true JPS6140755B2 (en) | 1986-09-10 |
Family
ID=12519267
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3822279A Granted JPS55130805A (en) | 1979-03-30 | 1979-03-30 | Manufacture of zinc selenide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS55130805A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4978577A (en) * | 1989-04-12 | 1990-12-18 | Cvd Incorporated | Method for preparing laminates of ZnSe and ZnS |
| US8765223B2 (en) | 2008-05-08 | 2014-07-01 | Air Products And Chemicals, Inc. | Binary and ternary metal chalcogenide materials and method of making and using same |
| US8507040B2 (en) | 2008-05-08 | 2013-08-13 | Air Products And Chemicals, Inc. | Binary and ternary metal chalcogenide materials and method of making and using same |
-
1979
- 1979-03-30 JP JP3822279A patent/JPS55130805A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS55130805A (en) | 1980-10-11 |
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