JPH02140924A - Manufacture of semiconductor device - Google Patents
Manufacture of semiconductor deviceInfo
- Publication number
- JPH02140924A JPH02140924A JP29363688A JP29363688A JPH02140924A JP H02140924 A JPH02140924 A JP H02140924A JP 29363688 A JP29363688 A JP 29363688A JP 29363688 A JP29363688 A JP 29363688A JP H02140924 A JPH02140924 A JP H02140924A
- Authority
- JP
- Japan
- Prior art keywords
- etching
- gasb
- substrate
- hno3
- solution
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000004065 semiconductor Substances 0.000 title claims description 6
- 238000005530 etching Methods 0.000 claims abstract description 57
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000000758 substrate Substances 0.000 abstract description 27
- 229910005542 GaSb Inorganic materials 0.000 abstract description 23
- 239000000243 solution Substances 0.000 abstract description 21
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 12
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 10
- 235000011149 sulphuric acid Nutrition 0.000 abstract description 6
- OEDMOCYNWLHUDP-UHFFFAOYSA-N bromomethanol Chemical compound OCBr OEDMOCYNWLHUDP-UHFFFAOYSA-N 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract 1
- MODGUXHMLLXODK-UHFFFAOYSA-N [Br].CO Chemical compound [Br].CO MODGUXHMLLXODK-UHFFFAOYSA-N 0.000 description 6
- 229910001868 water Inorganic materials 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- -1 Gallium antimony (GaSb) compound Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- CCJHDZZUWZIVJF-UHFFFAOYSA-N iodo nitrate Chemical compound [O-][N+](=O)OI CCJHDZZUWZIVJF-UHFFFAOYSA-N 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Weting (AREA)
Abstract
Description
【発明の詳細な説明】
〔概 要〕
ガリウムアンチモンの鏡面エツチングに関し、後処理が
必要なく鏡面仕上げができるエツチング液を提供するこ
とを目的とし、
Ｈ２Ｏ、ＨＮＯ３、）ＩＰ 、 Ｈ，ＳＯ，の混合液を
エツチング液として用いるように構成する。[Detailed Description of the Invention] [Summary] The purpose of this invention is to provide an etching solution that can produce a mirror finish without the need for post-processing for specular etching of gallium antimony. The etching solution is configured to be used as an etching solution.
本発明は半導体装置の製造方法に係り、より詳しく述べ
るとガリウムアンチモン基板表面をエピタキシャル成長
のために鏡面エツチング処理する方法に関する。The present invention relates to a method of manufacturing a semiconductor device, and more specifically to a method of mirror etching the surface of a gallium antimony substrate for epitaxial growth.
アバランシェホトダイオード（ＡＰＤ）の材料として、
その特性からガリウムアンチモン（ＧａＳｂ）化合物半
導体が有望視されている。典型的なＧａＳｂ −ＡＰＤ
は、第１図を参照すると、ｎ＋舟形ＧａＳｂ基板ｌ上、
ｎ−形ＧａＳｂ光吸収層２、ロー形Ａ ＲＧａＳｂ増倍
層３、ｎ−形Ａ ＲＧａＳｂウィンド層（ガードリング
層）４を連続エピタキシャル成長した後、ｎ−形へＲＧ
ａＳｂ層４内にドーピングしてｐ１形Ａ Ｉ ＧａＳｂ
領域５を形成した構造を有する。As a material for avalanche photodiode (APD),
Gallium antimony (GaSb) compound semiconductors are considered promising because of their characteristics. Typical GaSb-APD
Referring to FIG. 1, on an n+ boat-shaped GaSb substrate l,
After successive epitaxial growth of n-type GaSb light absorption layer 2, low-type A RGaSb multiplication layer 3, and n-type A RGaSb wind layer (guard ring layer) 4, RG to n-type
Doping the aSb layer 4 to form p1 type AI GaSb
It has a structure in which a region 5 is formed.
このようにＧａＳｂ基板上にエピタキシャル成長を行う
場合、ＧａＳｂ基板の表面が平滑でエッチピットなどが
存在しないことが要求される。しかしながら、エピタキ
シャル成長に用いる素材のＧａＳｂ基板は加工歪を有し
、そのままではエピタキシャル成長基板として用いるこ
とができないので、加工歪を除去するために通常厚み１
−以上にわたって鏡面エツチングを行う。When performing epitaxial growth on a GaSb substrate in this way, it is required that the surface of the GaSb substrate be smooth and free of etch pits. However, the GaSb substrate, which is the material used for epitaxial growth, has processing strain and cannot be used as an epitaxial growth substrate as it is.
- Perform mirror etching over the above steps.
従来、ＧａＳｂ基板のエツチング液としては、臭素をア
ルコールに溶解したブロムメタノール液と、ＨＦ ＋）
ＩＮＯ３＋ｃｕｆｆ［”ΩＯＨの混酸溶液とが代表的で
ある。Conventionally, etching solutions for GaSb substrates include a bromine methanol solution in which bromine is dissolved in alcohol, and HF +).
A mixed acid solution of INO3+cuff[''ΩOH is typical.
基板のエツチングの前にはトリクレン、アセトン、アル
コールで超音波洗浄を行う。その後硫酸（１分間）及び
塩酸（１分間）に浸漬し、プロメタエツチングの場合は
アルコールで置換し、その他のエツチング液の場合は純
水で水洗する。以上をエツチング前処理と称し、ＧａＳ
ｂ基板のエツチング前に必ず行う。Before etching the substrate, perform ultrasonic cleaning with trichloride, acetone, and alcohol. Thereafter, it is immersed in sulfuric acid (1 minute) and hydrochloric acid (1 minute), and in the case of prometha etching, the etching is replaced with alcohol, and in the case of other etching liquids, it is washed with pure water. The above is called etching pretreatment, and the GaS
Be sure to perform this before etching the b-substrate.
前処理後、ブロム１％を含むブロムメタノール液で１分
間攪拌しながらエツチングを行い、アルコール置換でエ
ツチングを終わる。以上がブロム−メタノールを用いた
ＧａＳｂのエツチングである。After the pretreatment, etching is performed with a bromine methanol solution containing 1% bromine while stirring for 1 minute, and the etching is completed by substitution with alcohol. The above is the etching of GaSb using bromine-methanol.
ところがＧａＳｂはその表面に容易に酸化膜が形成され
、前記エツチング前処理（ＨＣｊｌ！による）では、表
面の酸化膜が完全には除去しきれない。この様な基板を
ブロムメタノール液でエツチングした場合、酸化膜のあ
る所とない所でエツチング速度が異なり、その結果表面
が凸凹となり、肉眼で乳白色（ミルク・サーフエース）
を呈する状態となる問題がある。この様な基板を使用し
てエピタキシャル成長を行うと、成長界面が平滑でない
ため、ＡＰＤ素子化した時に暗電流増大等の素子特性の
悪化をまねくので不都合である。そのためブロムメタノ
ール液でエツチングした場合には、エピタキシャル成長
前にメルトバックする必要があり、煩雑である。However, an oxide film is easily formed on the surface of GaSb, and the oxide film on the surface cannot be completely removed by the etching pretreatment (based on HCjl!). When such a substrate is etched with a bromine methanol solution, the etching speed is different depending on where there is an oxide film and where it is not, and as a result, the surface becomes uneven and appears milky white (milk surface) to the naked eye.
There is a problem that results in a state where this occurs. If such a substrate is used for epitaxial growth, the growth interface will not be smooth, which is disadvantageous since it will lead to deterioration of device characteristics such as an increase in dark current when it is made into an APD device. Therefore, when etching is performed using a bromine methanol solution, it is necessary to perform melt-back before epitaxial growth, which is complicated.
また、ＨＦ ＋ ＨＮＯ，＋ＣＨ３Ｃ０ＤＨによるエツ
チングの場合にも、エツチング前処理は前記と同様に行
う。Further, in the case of etching using HF + HNO and +CH3C0DH, the etching pretreatment is performed in the same manner as described above.
ここでＧａＳｂはＮＨＯ，により非常に強固な酸化膜が
形成される事が知られている。ＨＦ ＋ ＨＮＯ３＋
ＣＨ３ＣＯ０Ｈ（１： ５ ：１０）溶液でエツチング
を行う場合、ＨＮＯ３の量が多いため、エツチング後強
固な酸化膜が形成されて残る。この様な基板を成長に使
用すると酸化膜が形成された所で未成長となり、良好な
エピタキシャル層を得る事が出来ない。またＡＰＤ素子
化した場合においてもブロム−メタノールでエツチング
した時と同様な特性の悪化を引き起こす。It is known that a very strong oxide film is formed on GaSb by NHO. HF + HNO3+
When etching is performed using a CH3CO0H (1:5:10) solution, a strong oxide film is formed and remains after etching because the amount of HNO3 is large. If such a substrate is used for growth, the oxide film will not grow where it was formed, making it impossible to obtain a good epitaxial layer. Further, even when an APD element is formed, the same deterioration of characteristics as that caused by etching with bromine-methanol is caused.
そこで、本発明は、上記のような不都合のない、すなわ
ち、平滑でエッチビットのない鏡面にＧａＳｂを仕上げ
ることができるエツチング液を提供することを目的とす
る。SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide an etching solution that can finish GaSb to a smooth, mirror-like surface without any etch bits, without the above-mentioned disadvantages.
上記目的の下、本発明によれば、ガリウムアンチモンに
対しＨ２Ｏ、）ＩＮＯ８，）ＩＰ 、 Ｈ２ＳＯ４の混
合液を用いて鏡面エツチングを施す工程を含むことを特
徴とする半導体装置の製造方法が提供される。According to the present invention, there is provided a method for manufacturing a semiconductor device, which includes a step of performing mirror etching on gallium antimony using a mixed solution of H2O, )INO8, )IP, and H2SO4. Ru.
本発明のエツチング液におけるＨ２Ｏ： ＨＮＯ３：
ＨＦ：Ｈ２ＳＯ４の比率は、原液として６１％のＨＮＯ
３，５０％のＨＦ及び９７％のＨ，Ｓ［］、を用いて、
一般に容積比で（１０〜８０） ： （０を含まず
１０以下）＝ （０を含まず１００以下）＝（０を含ま
ず５以下）であるが、ＨＦは常にＨＮＯ３より多く存在
すべきである。好ましい比率は２５ ：１０ ：２０
： ３である。本発明によるエツチング液はＨ２Ｏの量
を変える事によりエツチング速度を調節する事が可能で
ある。Ｈ２０の量を減らす事によりエツチング速度を速
くする事が出来る。しかし上記比率において１０未満に
すると、エツチング速度が速くなり過ぎ、基板表面にエ
ツチングむらを生じ、鏡面を得る事が不可能である。H2O in the etching solution of the present invention: HNO3:
The ratio of HF:H2SO4 is 61% HNO as stock solution.
Using 3,50% HF and 97% H,S[],
In general, the volume ratio is (10 to 80): (10 or less, not including 0) = (100 or less, not including 0) = (5 or less, not including 0), but HF should always be present in a larger amount than HNO3. be. The preferred ratio is 25:10:20
: It is 3. The etching rate of the etching solution according to the present invention can be adjusted by changing the amount of H2O. The etching speed can be increased by reducing the amount of H20. However, if the above ratio is less than 10, the etching rate becomes too high, causing uneven etching on the substrate surface, making it impossible to obtain a mirror surface.
Ｈ２Ｏ量を減らせばエツチング速度は遅くなり、８０超
混合するとほとんどエツチングされなくなる。ＨＮＯ３
１を変えてもエツチング速度は変化するが、１０超混合
してエツチング速度を速くする事は、酸化膜が形成され
る事を考えると好ましくない。１０以下とすればエツチ
ング速度が低下し、０でエツチングされなくなる。Ｈｆ
４１はＨＮＯ３１１とのバランスの問題である。すなわ
ち酸化膜形成を防ぐためにはつねにＨＮＯ３量より多い
事が必要であり、・２５以下として）ＩＮＯ，量に近づ
くほどエツチング速度は速くなるが、酸化膜が形成され
やすくなり、同量あるいはそれ以下とした場合には基板
全面に強固な酸化膜が形成され良好なエツチングが行え
ない。）ＩＰを２５超混合すれば、エツチング速度は低
下し、１００超ではほとんどエツチングされない。If the amount of H2O is reduced, the etching rate will be slowed down, and if the mixture exceeds 80%, etching will hardly occur. HNO3
Although the etching rate changes even if the number is changed by 1, it is not preferable to increase the etching rate by mixing more than 10, considering that an oxide film will be formed. If the value is 10 or less, the etching rate will decrease, and if it is 0, no etching will occur. Hf
41 is a problem of balance with HNO311. In other words, in order to prevent the formation of an oxide film, it is necessary that the amount of HNO3 is always greater than the amount of HNO3 (25 or less). In this case, a strong oxide film is formed over the entire surface of the substrate, making it impossible to perform good etching. ) If more than 25 IPs are mixed, the etching rate will decrease, and if more than 100 IPs are mixed, there will be hardly any etching.
Ｈ２ＳＯ４量は３〜４以下では良好な鏡面を得る事が出
来る。しかし５超混合した場合反応が速くなりすぎるた
め、基板表面に気泡を生じ良好な面を得る事は出来ない
。３未満にした場合エツチング速度が低下し、０ではほ
とんどエツチングされない。A good mirror surface can be obtained when the amount of H2SO4 is 3 to 4 or less. However, if more than 5 are mixed, the reaction becomes too fast, causing bubbles on the substrate surface, making it impossible to obtain a good surface. When it is less than 3, the etching rate decreases, and when it is 0, there is almost no etching.
本発明によるエツチング液は、ＧａＳｂがｌ（Ｆ＋ＨＮ
Ｏ。The etching solution according to the present invention has GaSb of 1(F+HN
O.
（＋８．０）溶液で溶解する事に着目し、ＧａＳｂ基板
表面を酸化させるＨＮＯ，の量を酸化膜形成が起こらな
い程度まで減らし、代わりにＨ，Ｓ０４を混合して、Ｈ
ＮＯ，量の低下によるエツチング速度の低下を補う様に
したものである。このため本発明によるエツチング液で
ＧａＳｂ基板をエツチングした場合、基板表面に酸化膜
の形成が起こらない。ゆえにブロムメタノール液でエツ
チングした時に生じる表面の凸凹（ミルク・サーフエー
ス）も発生しない。またピット等の発生も見られず非常
に平滑なエツチング面を得る事が出来る。(+8.0) Focusing on the fact that it dissolves in a solution, the amount of HNO, which oxidizes the GaSb substrate surface, was reduced to the extent that oxide film formation did not occur, and instead, HNO and S04 were mixed.
This is designed to compensate for the decrease in etching speed due to the decrease in the amount of NO. Therefore, when a GaSb substrate is etched with the etching solution according to the present invention, no oxide film is formed on the substrate surface. Therefore, the surface unevenness (milk surface) that occurs when etching with bromo-methanol solution does not occur. Moreover, no pits or the like are observed, and a very smooth etched surface can be obtained.
ＧａＳｂ基板はアルコール、アセトン、トリクレン等で
超音波洗浄し、硫酸に１分間浸漬した後、塩酸に１分間
浸漬する前処理を行う。The GaSb substrate is subjected to pretreatment by ultrasonically cleaning with alcohol, acetone, trichlene, etc., immersed in sulfuric acid for 1 minute, and then immersed in hydrochloric acid for 1 minute.
次に本発明によるエツチング液を攪はんしなからＧａＳ
ｂ基板を浸漬する。ここで液組成とその組成におけるエ
ッチレートを示す。Next, without stirring the etching solution according to the present invention,
b Immerse the substrate. Here, the liquid composition and the etch rate for that composition are shown.
１’＋２０ ： ＨＮＯ３： ｔｌＦ ： Ｈ２ＳＯ４
２５： １０ ：２０： ３
エツチレート ３ｐ／ｍｉｎ
エッチレートからエツチング時間は２０秒以上であれば
加工ヒズミ層を除去出来る。1'+20: HNO3: tIF: H2SO4
25: 10: 20: 3 Etching rate: 3 p/min If the etching time is 20 seconds or more, the processed distortion layer can be removed.
本発明によるエツチング液を使用すればＧａＳｂ基板に
平滑でピットのない鏡面エツチングを施す事が出来る。By using the etching solution according to the present invention, a GaSb substrate can be etched to a smooth, pit-free mirror surface.
本発明によればＧａＳｂ基板の鏡面エツチングにおいて
、酸化膜塑成のない鏡面状態のまま加工ヒズミ層を除去
する事が出来、高品質のＡＰＤ素子等の半導体装置の製
造が可能となる。According to the present invention, in the mirror etching of a GaSb substrate, it is possible to remove the processing strain layer while maintaining the mirror surface without forming an oxide film, thereby making it possible to manufacture high quality semiconductor devices such as APD elements.
第１図はＧａＳｂ基板を用いたＡＰＤの断面図、である
。
図において
１はｎ”ＧａＳｂ基板、
２はｎ −・Ｇ ａ Ｓ ｂ光吸収層、３はｎ−ΔβＧ
ａＳｂ増倍層、
４はｎ−ＡβＧａＳｂウィンド層（ガードリング層）、
５ は Ｐ”八βＧａＳｂ０
ｈｌ）FIG. 1 is a cross-sectional view of an APD using a GaSb substrate. In the figure, 1 is an n''GaSb substrate, 2 is an n-GaSb light absorption layer, and 3 is n-ΔβG.
aSb multiplication layer, 4 is n-AβGaSb wind layer (guard ring layer),
5 is P”8βGaSb0 hl)
Claims (1)
ＨＦ、Ｈ＿２ＳＯ＿４の混合液を用いて鏡面エッチング
を施す工程を含むことを特徴とする半導体装置の製造方
法。1. H_2O, HNO_3 for gallium antimony,
A method for manufacturing a semiconductor device, comprising a step of performing mirror etching using a mixed solution of HF and H_2SO_4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29363688A JPH02140924A (en) | 1988-11-22 | 1988-11-22 | Manufacture of semiconductor device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29363688A JPH02140924A (en) | 1988-11-22 | 1988-11-22 | Manufacture of semiconductor device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02140924A true JPH02140924A (en) | 1990-05-30 |
Family
ID=17797276
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29363688A Pending JPH02140924A (en) | 1988-11-22 | 1988-11-22 | Manufacture of semiconductor device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02140924A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1213371A2 (en) * | 2000-11-20 | 2002-06-12 | Universite Laval | Surface chemical treatment for liquid gallium or gallium alloy mirrors |
-
1988
- 1988-11-22 JP JP29363688A patent/JPH02140924A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1213371A2 (en) * | 2000-11-20 | 2002-06-12 | Universite Laval | Surface chemical treatment for liquid gallium or gallium alloy mirrors |
| EP1213371A3 (en) * | 2000-11-20 | 2002-06-19 | Universite Laval | Surface chemical treatment for liquid gallium or gallium alloy mirrors |
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