JPH025578A - Manufacture of light emitting element - Google Patents
Manufacture of light emitting elementInfo
- Publication number
- JPH025578A JPH025578A JP63156138A JP15613888A JPH025578A JP H025578 A JPH025578 A JP H025578A JP 63156138 A JP63156138 A JP 63156138A JP 15613888 A JP15613888 A JP 15613888A JP H025578 A JPH025578 A JP H025578A
- Authority
- JP
- Japan
- Prior art keywords
- heat treatment
- light emitting
- thin film
- group
- temperature
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 30
- 239000007789 gas Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 239000012298 atmosphere Substances 0.000 claims abstract description 12
- 239000011261 inert gas Substances 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 239000013078 crystal Substances 0.000 claims description 19
- 239000010409 thin film Substances 0.000 claims description 16
- 238000005468 ion implantation Methods 0.000 claims description 12
- 239000002019 doping agent Substances 0.000 claims description 3
- 239000011701 zinc Substances 0.000 abstract description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052725 zinc Inorganic materials 0.000 abstract description 8
- 238000002513 implantation Methods 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 7
- 229910001218 Gallium arsenide Inorganic materials 0.000 abstract description 6
- 239000012299 nitrogen atmosphere Substances 0.000 abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 2
- 238000000137 annealing Methods 0.000 abstract description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 2
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 abstract 3
- 229910000927 Ge alloy Inorganic materials 0.000 abstract 1
- 229910001245 Sb alloy Inorganic materials 0.000 abstract 1
- 230000002159 abnormal effect Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 12
- 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 description 10
- 230000007547 defect Effects 0.000 description 8
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- AXAZMDOAUQTMOW-UHFFFAOYSA-N dimethylzinc Chemical compound C[Zn]C AXAZMDOAUQTMOW-UHFFFAOYSA-N 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000005083 Zinc sulfide Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910052984 zinc sulfide Inorganic materials 0.000 description 3
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 229910017401 Au—Ge Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical group CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 description 1
- 229910000058 selane Inorganic materials 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 125000003748 selenium group Chemical group *[Se]* 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Led Devices (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はＩＩ−ＶＩ族化合物を用いた発光素子の製造方
法に関し、特に亜鉛を含むＩｔ−ＶＩ族化合物を用いた
青色発光素子の製造方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for manufacturing a light emitting device using a II-VI group compound, and particularly a method for manufacturing a blue light emitting device using an It-VI group compound containing zinc. Regarding.
従来からシリコンや砒化ガリウムの伝導形制御の一方法
としてイオン注入法が知られている。Ion implantation has been known as a method for controlling the conductivity of silicon and gallium arsenide.
方、セレン化亜鉛あるいは硫化亜鉛単結晶薄膜はｐ形の
形成法が充分に確立されておらず、−手段としてイオン
注入法が考えられるが、具体的な条件等はほとんど知ら
れていない。特にイオン注入後の熱処理によって注入に
よる損傷をとり除きかつ亜鉛空孔や■族空孔の固有欠陥
を発生することなく注入原子が電気伝導に寄与する割合
（活性化率）を向上させるための条件はほとんど明らか
にされていない。また上記の条件だけでなく、イオン注
入を行う結晶薄膜に要求される品質、例えば化学量論比
などについてもほとんど検討されていない。On the other hand, the method for forming p-type zinc selenide or zinc sulfide single-crystal thin films has not been sufficiently established, and although ion implantation is a possible method, little is known about the specific conditions. In particular, conditions for removing damage caused by implantation through heat treatment after ion implantation and improving the ratio at which implanted atoms contribute to electrical conduction (activation rate) without generating inherent defects such as zinc vacancies and group III vacancies. is hardly revealed. Furthermore, in addition to the above-mentioned conditions, little consideration has been given to the quality required for the crystalline thin film into which ions are implanted, such as the stoichiometric ratio.
一般に結晶に対してイオン注入により不純物の添加を行
えば、それによる結晶の損傷は避けられず、これを回復
させ、注入した不純物を有効に電気伝導に寄与させるた
めには、何らかの熱処理工稈が不可欠である。しかしこ
、−でセレン化亜鉛結晶薄膜の場合はつぎのような問題
点をかかえている。すなわちセし・ン化亜鉛単結晶薄膜
を気相成長させる場合、成長温度を２００−＝−４００
℃という低温に設定しないと固有欠陥が発生し、結晶の
晶質低下を招く。また、この薄膜の化学量論比が正しく
保たれていないと、上記成長温度程度の低温熱処理によ
っても固有欠陥に起因する深い準位が容易に発生ずる。Generally, when impurities are added to a crystal by ion implantation, damage to the crystal is unavoidable, and in order to recover from this and make the implanted impurities effectively contribute to electrical conduction, some kind of heat treatment process is required. It is essential. However, in the case of zinc selenide crystal thin films, the following problems arise. In other words, when growing a zinc oxide single crystal thin film in a vapor phase, the growth temperature is set to 200-=-400.
If the temperature is not set at a low temperature of °C, inherent defects will occur, leading to a decrease in the quality of the crystal. Further, if the stoichiometric ratio of this thin film is not maintained correctly, deep levels caused by intrinsic defects will easily occur even by low-temperature heat treatment at about the above-mentioned growth temperature.
したがってセし・ン化亜鉛に不純物をイオン注入し、結
晶の品質を）員わずにｐ形伝導を得ることは極めて困難
であるという重大な問題点があった。Therefore, there was a serious problem in that it was extremely difficult to obtain p-type conduction without affecting the quality of the crystal by implanting impurity ions into zinc selenide.
〔課題を解決するための手段］
本発明は十記従来の問題点を解決するためになされたも
のであって、単結晶基板上に低抵抗ｎ型ＩＩ−ＶＩ族化
合物華結晶薄膜をエピタキシャル成長さ−ぜる工程、該
低抵抗単結晶薄膜上にノンドープの高抵抗ＩＩ−ＶＩ族
化合物単結晶薄膜をエピタキシャル成長さセる工程、該
高抵抗単結晶薄膜に・イオン注入法を用いてｐ型ドーパ
ントを添加する工程、及び該１乙−バントを添加した準
結晶薄膜を熱処理する工程を含む発光素子の製造方法に
おいて、該熱処理が不活性ガスおよび／ま／＋−８Ｊ、
■族元素を含むガスの雰囲気下で、５５０〜８００℃の
温度でおこなっている。[Means for Solving the Problems] The present invention has been made in order to solve ten conventional problems, and is a method of epitaxially growing a low-resistance n-type II-VI group compound flower crystal thin film on a single crystal substrate. - a step of epitaxially growing a non-doped, high-resistance II-VI group compound single-crystal thin film on the low-resistance single-crystal thin film; and a step of heat-treating the quasi-crystalline thin film to which the 1B-Bant is added, wherein the heat treatment is performed using an inert gas and/or /+-8J,
The process is carried out at a temperature of 550 to 800°C in an atmosphere of gas containing group (1) elements.
本発明においては、熱処理を■不活性ガスおよび／また
は■族元素台むガスの雰囲気で０５５０〜８００℃の熱
処理とし２ているが、両方の条件がそろわないと良好な
発光機能を存する発光素子は得られない。In the present invention, the heat treatment is performed at 0550 to 800°C in an atmosphere of an inert gas and/or a gas containing a group II element, but if both conditions are not met, the light-emitting element will not have good light-emitting function. cannot be obtained.
５５０℃よりも低い熱処理では、イオン注入により生じ
た損傷は回復されず、ドーパントは活性化されない。５
５０〜８００℃の熱処理であっても不活性ガスおよび／
または■族元素を含むガスの雰囲気下でな％ｊれば、ｎ
−ｖｔ族化合物半汚体薄膜中にかえって欠陥が生じて（
〜まい、良好な発光機能を有する発光素子は得られない
、８００℃よりも高い熱処理では、例え不活性ガスおよ
び７才たは■族元素を含むガスの雰囲気下であっても薄
膜中にかえって欠陥を生ずることになる。Heat treatments below 550° C. do not repair the damage caused by the ion implantation and do not activate the dopant. 5
Even during heat treatment at 50 to 800°C, inert gas and/or
Or in an atmosphere of gas containing group ■ elements, n
-Defects are instead generated in the semi-filtered thin film of the VT group compound (
- No, a light-emitting element with good light-emitting function cannot be obtained. Heat treatment at temperatures higher than 800°C will result in the formation of light-emitting elements in the thin film even under an atmosphere of an inert gas and a gas containing Group 7 or Group II elements. This will result in defects.
熱処理時間は、熱処理温度およびイオン注入量等により
調整されるが通常１分以上６時間以内とすることが好ま
しい。The heat treatment time is adjusted depending on the heat treatment temperature, the amount of ion implantation, etc., but it is usually preferably 1 minute or more and 6 hours or less.
又不活性ガスおよび／または■族元素を含むガスの雰囲
気は、加圧１常圧、？Ｉｉ圧等任意の圧力下でかまわな
いが、常圧下とすることが設備的な面や欠陥の発生防止
等の面で好ましい。In addition, the atmosphere of the gas containing the inert gas and/or the group Ⅰ element is pressurized to normal pressure, ? Although any pressure such as Ii pressure may be used, it is preferable to use normal pressure from the viewpoint of equipment and prevention of defects.
又該処理温度は比較的高い力がより高ン震度Ｇこ注入さ
れてヰした欠陥を回復できるので好ましく、６２０−７
６０℃とすることが望まＬ７い。Also, the treatment temperature is preferable because a relatively high force can be injected with a higher seismic intensity G to recover the damaged defects, and 620-7
It is desirable to set the temperature to 60°C.
該熱処理は、不活性ガスおよび／′または■族元素を′
Ａむガス雰囲気下でおこなわれるが、不活性ガスとして
ばＮ２ ＋ Ｉｌｅ ＋ Ｎｅ ＋ Ａｒ等が、■族元
素を含むガスと１−ではジメチル亜鉛、ジエチル亜鉛。The heat treatment is carried out using an inert gas and /' or group II elements.
The inert gas is N2 + Ile + Ne + Ar, etc., and the gas containing Group Ⅰ elements is dimethylzinc, diethylzinc.
亜鉛単体等が例示できる。An example is zinc alone.
■族元素を含むガスを使用する場合には、使用される＋
１−Ｖｌ族化合物の＋１族元素を使用する、−とが好ま
しい。■When using gas containing group elements, +
1-Using +1 group element of Vl group compound, - is preferred.
又■族元素を含むガス雰囲気を使用Ｊ゛る場合には、該
ガスの１００％雰囲気としてもかまわないが、常圧下で
熱処理するためには、８５ ＋１族元素を含むガスを１
０−５ｍｏｌＺ以上とすることが好ましい。In addition, if a gas atmosphere containing group Ⅰ elements is used, the atmosphere may be 100% of the gas, but in order to perform heat treatment under normal pressure, 100% of the gas containing 85 + group 1 elements is used.
It is preferable to set it as 0-5 molZ or more.
本発明によれば、セレン化亜鉛発光素子の製造において
、イオン注入法によるｐ型膜を得るためには、ますもと
になるイオン注入前の膜の量論比を高く保つことによっ
て、また、熱処理条件のなかでも雰囲気ガスとして窒素
等の不活性ガスが、■族元素（亜鉛）空孔を抑える為に
■族元素（亜鉛）蒸気を含む雰囲気で熱処理４−る事に
より、深い準位の起源である■族元素（亜鉛）空孔の発
生を抑えて８００℃まで熱処理できる。その為、注入に
よる損傷は処理温度４５０℃以上にすると注入された膜
の損傷は徐々に回復しはじめ、熱処理温度の増加ととも
に、固有欠陥（Ｚｎの空孔に関与した深い準位）を発生
させずに急激損傷は取り除かれ、注入原子も、活性化す
ることができるので膜はｐ型伝導を示す。According to the present invention, in manufacturing a zinc selenide light emitting device, in order to obtain a p-type film by ion implantation, by keeping the stoichiometric ratio of the original film before ion implantation high, and Among the heat treatment conditions, an inert gas such as nitrogen is used as the atmospheric gas, and the heat treatment is performed in an atmosphere containing group III element (zinc) vapor to suppress group III element (zinc) vacancies, thereby creating deep levels. Heat treatment can be performed up to 800°C while suppressing the generation of vacancies caused by the group Ⅰ element (zinc), which is the origin of the process. Therefore, damage caused by implantation begins to gradually recover when the treatment temperature is increased to 450°C or higher, and as the heat treatment temperature increases, intrinsic defects (deep levels associated with Zn vacancies) are generated. The rapid damage is removed without any damage, and the implanted atoms can also be activated, so that the film exhibits p-type conduction.
第３図および第４図は本発明により作成した発光素子の
構造を示す断面図である。FIGS. 3 and 4 are cross-sectional views showing the structure of a light emitting device produced according to the present invention.
第３図は単結晶基板としてｎ型ＧａＡｓ （１００）基
板またはＺｎ５ｅ （１００）基板が使われた時のＺｎ
５ｅのｐ−ｎ接合を利用したデバイス構造を示した１例
である。Figure 3 shows Zn when an n-type GaAs (100) substrate or Zn5e (100) substrate is used as the single crystal substrate.
This is an example of a device structure using a pn junction of 5e.
これに対し、第４図は、ｐ型ＧａＡｓ （１００）基板
６を用いた場合の青色発光素子のデバイスの構造を示し
である。どちらも基板の面方位は（１００）面でもよい
しく１００）から＜１）０＞へ２″〜５゜オフしていて
もかまわない。膜の成長条件は、特開昭６３−７９７９
５に詳細に述べであるが、成長温度２５０℃、管内圧力
は常圧で成長を行ない、■族原料ガスとしてはセレン化
水素、■族原料としてはジメチル亜鉛を使い、そのモル
流量比（亜鉛に対するセレンの比）は２０に保つのであ
る。またジメチル亜鉛の流量は１）．５Ｘ １０−６モ
ル／分でありキャリアガスの水素で３リツタ一／分に着
起されて作製される。またｎ型Ｚｎ５ｅ ２は、Ｉ Ｑ
Ｉ ＩＩ ｃｍ −３の電子濃度をもつ膜である。ま
たドーピングのガスとしてはｔＢｕ−１（ターシナルブ
チルヨウ素）もしくはＥｔｌ （エチルヨウ素）、ヨウ
化水素、塩化水素等が用いられる。On the other hand, FIG. 4 shows the structure of a blue light emitting device using a p-type GaAs (100) substrate 6. In both cases, the plane orientation of the substrate may be the (100) plane, or may be off by 2" to 5 degrees from 100) to <1)0>. The film growth conditions are as described in Japanese Patent Application Laid-Open No. 63-7979.
As described in detail in Section 5, the growth was carried out at a growth temperature of 250°C and a pressure inside the tube of normal pressure. Hydrogen selenide was used as the group III raw material gas, dimethyl zinc was used as the group III raw material, and their molar flow rate ratio (zinc The ratio of selenium to carbon dioxide is kept at 20. Also, the flow rate of dimethylzinc is 1). 5×10 −6 mol/min, and is produced by plating at 3 liters/min with hydrogen as a carrier gas. In addition, n-type Zn5e 2 has IQ
It is a film with an electron concentration of I II cm −3. Further, as the doping gas, tBu-1 (tertiary butyl iodine), Etl (ethyl iodine), hydrogen iodide, hydrogen chloride, etc. are used.
以下に第３図に示す発光素子の製造工程を説明する。The manufacturing process of the light emitting device shown in FIG. 3 will be explained below.
ｎ型ＧａＡｓ基板ｌ上にｎ型Ｚｎ５ｅ ２をバッファ層
として約０．３μｍ程度成長した後、高抵抗のノンドー
プＺｎ５ｅ層３を約０．３μｍ成長させる。その後、こ
の高抵抗のノンドープＺｎ５ｅ層３にリチウムイオンを
加速電圧５０ｋｅＶ、イオン電流８０μＡでドーズＮ
１０ ”ｃｍ−２程度注入する。注入後、基板をアニー
ル炉に入れて７５７℃、５分常圧の窒素雰囲気（流量４
リツタ一／分）で熱処理する。第１図はこれをフォトル
ミネッセンスで評価したものであり、処理しないものは
青色発光を示していない。しかし、４５１℃、５分の熱
処理でわずかに青色発光を示しはじめ熱処理を６５７℃
でおこなうと急激に青色発光の強度が増加しており、注
入による損傷が回復している事がわかる。さらに温度を
７５７℃にあげるとリチウムによる青色発光が一段と強
くなり、処理しないものと比べると約１万倍も増加する
。これは、７００℃程度以上で熱処理する事によってリ
チウム原子が膜中で活性化している事を示すものである
。After growing n-type Zn5e 2 as a buffer layer to a thickness of about 0.3 μm on an n-type GaAs substrate 1, a high resistance non-doped Zn5e layer 3 is grown to a thickness of about 0.3 μm. After that, lithium ions were dosed into this high resistance non-doped Zn5e layer 3 at an acceleration voltage of 50 keV and an ion current of 80 μA.
Inject approximately 10"cm-2. After implantation, the substrate is placed in an annealing furnace at 757°C for 5 minutes in a nitrogen atmosphere at normal pressure (flow rate 4
Heat-treated at Rituta 1/min). FIG. 1 shows an evaluation of this using photoluminescence, and the untreated sample did not emit blue light. However, after heat treatment at 451℃ for 5 minutes, a slight blue light emission started to appear and after heat treatment at 657℃.
When the injection was performed, the intensity of the blue light emission increased rapidly, indicating that the damage caused by the injection had been recovered. Furthermore, when the temperature is raised to 757 degrees Celsius, the blue light emitted by lithium becomes even stronger, increasing by about 10,000 times compared to the untreated material. This indicates that lithium atoms are activated in the film by heat treatment at about 700° C. or higher.
また、雰囲気ガスとしてジメチル亜鉛（ＤＭＺ）を１０
−５モル／分含む水素キャリアガス（４１／分）の雰囲
気下で７００’Ｃ，５分熱処理を施しても、第１図の７
５７℃、５分窒素雰囲気中で熱処理した場合と同様、Ｚ
ｎの空孔に関与した深い準位の発生を抑制し、リチウム
原子を活性化できる。In addition, dimethyl zinc (DMZ) was added as an atmospheric gas at 10%
Even if heat treatment is performed at 700'C for 5 minutes in an atmosphere of hydrogen carrier gas (41/min) containing -5 mol/min, the
Z
It is possible to suppress the generation of deep levels associated with n vacancies and activate lithium atoms.
この熱処理後、サンプルの上面にＡｕ−５ｂ合金４を蒸
着し、下面にはＡｕ−Ｇｅ合金５をオーミック電極とし
て蒸着する。After this heat treatment, an Au-5b alloy 4 is deposited on the upper surface of the sample, and an Au-Ge alloy 5 is deposited on the lower surface as an ohmic electrode.
このようにして作製された青色発光素子に電流注入した
ときの発光時性を第２図に示す。深い単位を介した長波
長域の発光のない強い青色発光が得られた。FIG. 2 shows the luminescence characteristics when a current is injected into the blue light emitting device manufactured in this way. Strong blue light emission without long wavelength emission through deep units was obtained.
以下に第４図に示す発光素子の製造工程を説明する。The manufacturing process of the light emitting device shown in FIG. 4 will be explained below.
ｐ型ＧａＡｓ基板６上に高抵抗ノンドープＺｎ５ｅ膜３
を０．３μｍ成長した後、リチウムを５０ｋｅＶ３Ｑμ
ＡでＩ Ｑ” Ｃｌ１）−”イオン注入する。注入後、
サンプルを窒素雰囲気中で７５７℃、５分熱処理し、リ
チウム原子を活性化させｐ層を得る。その後、ふたたび
基板を反応室に入れｎ型のＺｎ５ｅ層２を約３μｍ程度
成長させ、上面にはＡｕ／Ｉｎのオーミック電極７を、
下面にはＡｕ／Ｚｎのオーミック電極８を形成する。High resistance non-doped Zn5e film 3 on p-type GaAs substrate 6
After growing 0.3μm of lithium, 50keV3Qμ
I Q"Cl1)-" ions are implanted at A. After injection,
The sample is heat-treated at 757° C. for 5 minutes in a nitrogen atmosphere to activate lithium atoms and obtain a p-layer. After that, the substrate was placed in the reaction chamber again and an n-type Zn5e layer 2 was grown to a thickness of about 3 μm, and an Au/In ohmic electrode 7 was placed on the top surface.
An ohmic electrode 8 of Au/Zn is formed on the lower surface.
このようにして作製した青色発光素子も第２図とほぼ同
じ強い青色発光を呈する。The blue light emitting device thus produced also emits strong blue light almost the same as that shown in FIG.
なお、注入によるダメージの回復に要する熱処理温度は
注入ドーズ世に依存しており、ｌ Ｑ １３ ｃ「２以
下では熱処理温度４５０℃でも十分に不純物は活性化す
るのに対し、ＩＱ”ｃｍ−２以上になると５００°Ｃで
も損傷は回復せず、少なくとも５５０℃以上でなければ
回復しない。また、このような高温度のイオン注入では
、不純物の活性化は温度とともに急激に増大し、８００
℃付近で最大になるが、膜からセレン原子が蒸発をしは
じめ、膜の表面は荒れる膜質が劣化する為、青色発光強
度も急激に低下する。Note that the heat treatment temperature required to recover from damage caused by implantation depends on the implantation dose, and impurities are sufficiently activated even at a heat treatment temperature of 450°C at lQ13c'2 or lower, whereas at IQ'cm-2 or higher, At that point, the damage will not recover even at 500°C, and will not recover unless the temperature is at least 550°C or higher. In addition, in such high-temperature ion implantation, the activation of impurities increases rapidly with temperature, and
It reaches its maximum at around ℃, but as selenium atoms begin to evaporate from the film and the surface of the film becomes rough, the quality of the film deteriorates, and the intensity of blue light emission also drops rapidly.
この実施例ではセレン化亜鉛について説明したが、これ
は硫化亜鉛もしくはセレン化亜鉛と硫化亜鉛の混晶にお
いても適用できる。また注入イオンはリチウムに限らず
、ナトリウム、カリウム、また■族の窒素、燐、砒素、
アンチモン等であってもよい。熱処理の雰囲気は常圧で
あることが望ましいが、減圧でも可能である。またオー
ミック電極用金属材料は上記のものに限らず、ｎ形、ｐ
形に対してそれぞれオーミック接触が形成できる材料で
あればよい。In this example, zinc selenide has been described, but this can also be applied to zinc sulfide or a mixed crystal of zinc selenide and zinc sulfide. In addition, the implanted ions are not limited to lithium, but also sodium, potassium, nitrogen, phosphorus, arsenic, etc.
It may also be antimony or the like. The atmosphere for the heat treatment is preferably normal pressure, but reduced pressure is also possible. Furthermore, metal materials for ohmic electrodes are not limited to those mentioned above, but include n-type, p-type,
Any material may be used as long as it can form ohmic contact with each shape.
本発明によれば、従来までイオン注入法によるｐ型セレ
ン化亜鉛ひいては、ｐ−ｎ接合をつかった青色発光素子
について、まったく検討すらされていなかった。膜の作
製条件及びイオン注入後の熱処理条件を上記の条件に設
定する事により、注入によるダメージを取り除き、固有
欠陥やそれに起因した深い準位を発生させないで注入イ
オンを活性化できる事が可能となり、ｐ型セレン化亜鉛
が作製でき、ｐ−ｎ接合を利用したセレン化亜鉛青色発
光素子が実現できる。According to the present invention, until now, p-type zinc selenide produced by ion implantation, and even a blue light-emitting element using a pn junction, have not even been considered at all. By setting the film fabrication conditions and the heat treatment conditions after ion implantation to the above conditions, it is possible to remove damage caused by implantation and activate implanted ions without generating intrinsic defects or deep levels caused by them. , p-type zinc selenide can be produced, and a zinc selenide blue light-emitting device using a p-n junction can be realized.
【図面の簡単な説明】
第１図は熱処理温度の変化によるセレン化亜鉛膜のフォ
トルミネッセンススペクトルの変化を示す図、第２図は
実施例で作製した発光素子の発光スペクトルを示す図、
第３図および第４図は実施例で作製した発光素子の概略
を示す断面図である。
特許出願人 日本板硝子株式会社[Brief Description of the Drawings] Fig. 1 is a diagram showing changes in the photoluminescence spectrum of a zinc selenide film due to changes in heat treatment temperature, Fig. 2 is a diagram showing the emission spectrum of a light emitting device produced in an example,
FIGS. 3 and 4 are cross-sectional views schematically showing the light emitting devices manufactured in Examples. Patent applicant Nippon Sheet Glass Co., Ltd.
Claims (1)
薄膜をエピタキシャル成長させる工程、該低抵抗単結晶
薄膜上にノンドープの高抵抗II−VI族化合物単結晶薄膜
をエピタキシャル成長させる工程、該高抵抗単結晶薄膜
にイオン注入法を用いてｐ型ドーパントを添加する工程
、及び該ドーパントを添加した単結晶薄膜を熱処理する
工程を含む発光素子の製造方法において、該熱処理が不
活性ガスおよび／またはII族元素を含むガスの雰囲気下
で、５５０〜８００℃の温度でおこなわれることを特徴
とする発光素子の製造方法。(1) epitaxially growing a low resistance n-type II-VI group compound single crystal thin film on a single crystal substrate; epitaxially growing a non-doped high resistance II-VI group compound single crystal thin film on the low resistance single crystal thin film; A method for manufacturing a light emitting device, which includes a step of adding a p-type dopant to the high-resistance single-crystal thin film using an ion implantation method, and a step of heat-treating the single-crystal thin film to which the dopant has been added, wherein the heat treatment is performed using an inert gas and A method for manufacturing a light emitting device, characterized in that the process is carried out at a temperature of 550 to 800° C. in an atmosphere of a gas containing a group II element.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15613888A JP2561321B2 (en) | 1988-06-24 | 1988-06-24 | Method of manufacturing light emitting device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15613888A JP2561321B2 (en) | 1988-06-24 | 1988-06-24 | Method of manufacturing light emitting device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH025578A true JPH025578A (en) | 1990-01-10 |
| JP2561321B2 JP2561321B2 (en) | 1996-12-04 |
Family
ID=15621160
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15613888A Expired - Lifetime JP2561321B2 (en) | 1988-06-24 | 1988-06-24 | Method of manufacturing light emitting device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2561321B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5215929A (en) * | 1990-11-29 | 1993-06-01 | Matsushita Electric Industrial Co., Ltd. | Method of manufacturing pn-junction device II-VI compound semiconductor |
-
1988
- 1988-06-24 JP JP15613888A patent/JP2561321B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5215929A (en) * | 1990-11-29 | 1993-06-01 | Matsushita Electric Industrial Co., Ltd. | Method of manufacturing pn-junction device II-VI compound semiconductor |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2561321B2 (en) | 1996-12-04 |
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