JP5767796B2 - Etching solution composition and etching method - Google Patents
Etching solution composition and etching method Download PDFInfo
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- JP5767796B2 JP5767796B2 JP2010217421A JP2010217421A JP5767796B2 JP 5767796 B2 JP5767796 B2 JP 5767796B2 JP 2010217421 A JP2010217421 A JP 2010217421A JP 2010217421 A JP2010217421 A JP 2010217421A JP 5767796 B2 JP5767796 B2 JP 5767796B2
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- 238000005530 etching Methods 0.000 title claims description 158
- 239000000203 mixture Substances 0.000 title claims description 77
- 238000000034 method Methods 0.000 title claims description 39
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- -1 organic acid salts Chemical class 0.000 claims description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 150000007524 organic acids Chemical class 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 150000007522 mineralic acids Chemical class 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- 150000002736 metal compounds Chemical class 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000002280 amphoteric surfactant Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 7
- 150000007513 acids Chemical class 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 235000005985 organic acids Nutrition 0.000 claims description 5
- 239000003945 anionic surfactant Substances 0.000 claims description 4
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 4
- 239000002736 nonionic surfactant Substances 0.000 claims description 4
- YNVZDODIHZTHOZ-UHFFFAOYSA-K 2-hydroxypropanoate;iron(3+) Chemical compound [Fe+3].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O YNVZDODIHZTHOZ-UHFFFAOYSA-K 0.000 claims description 3
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 3
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 3
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 3
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 claims description 3
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 3
- 150000003009 phosphonic acids Chemical class 0.000 claims description 3
- 150000003460 sulfonic acids Chemical class 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 52
- 239000004065 semiconductor Substances 0.000 description 23
- 239000000758 substrate Substances 0.000 description 11
- 238000000605 extraction Methods 0.000 description 10
- 235000011054 acetic acid Nutrition 0.000 description 6
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 5
- 238000001312 dry etching Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000007788 roughening Methods 0.000 description 3
- 229910000980 Aluminium gallium arsenide Inorganic materials 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JLLMDXDAVKMMEG-UHFFFAOYSA-N hydrogen peroxide phosphoric acid Chemical compound OO.OP(O)(O)=O JLLMDXDAVKMMEG-UHFFFAOYSA-N 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- BYMMIQCVDHHYGG-UHFFFAOYSA-N Cl.OP(O)(O)=O Chemical compound Cl.OP(O)(O)=O BYMMIQCVDHHYGG-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-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
- LDLSHWGVWQXQMZ-UHFFFAOYSA-N OO.Cl.S(O)(O)(=O)=O.C(C)(=O)O Chemical compound OO.Cl.S(O)(O)(=O)=O.C(C)(=O)O LDLSHWGVWQXQMZ-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- UDOZVPVDQKQJAP-UHFFFAOYSA-N trifluoroamine oxide Chemical class [O-][N+](F)(F)F UDOZVPVDQKQJAP-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/005—Processes
- H01L33/0095—Post-treatment of devices, e.g. annealing, recrystallisation or short-circuit elimination
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/20—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a particular shape, e.g. curved or truncated substrate
- H01L33/22—Roughened surfaces, e.g. at the interface between epitaxial layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/005—Processes
- H01L33/0062—Processes for devices with an active region comprising only III-V compounds
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- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Weting (AREA)
- ing And Chemical Polishing (AREA)
- Led Devices (AREA)
Description
本発明はエッチング組成物およびそれを用いたエッチング方法に関し、詳しくは、発光ダイオード(以下、「LED」という)の光取り出し面などに用いられる半導体膜をエッチングするためのエッチング液およびそれを用いたエッチング方法に関する。 The present invention relates to an etching composition and an etching method using the same, and more specifically, an etching solution for etching a semiconductor film used for a light extraction surface of a light emitting diode (hereinafter referred to as “LED”) and the like. The present invention relates to an etching method.
LEDは、一般に高い発光効率が要求される。そして、LEDの発光効率は、内部量子効率と光取り出し効率の積によって決まる。そのため、発光効率を高めようとすると、この数値を増加させることが必要になる。 The LED is generally required to have high luminous efficiency. The luminous efficiency of the LED is determined by the product of the internal quantum efficiency and the light extraction efficiency. Therefore, to increase the luminous efficiency, it is necessary to increase this value.
このうち、光取り出し効率を向上させる技術として、光取り出し面となる半導体膜の表面に凹凸を形成する加工(粗面化処理)を行い、光の反射を抑えて向上させる方法が提案されている。 Among these, as a technique for improving the light extraction efficiency, a method for improving the light reflection by suppressing the reflection of light by performing a process (roughening process) for forming irregularities on the surface of the semiconductor film serving as the light extraction surface has been proposed. .
ところで、近年は、黄緑〜赤色の高輝度LEDにおいては、AlGaInP膜が利用されている。そして、このAlGaInP膜(半導体膜)の表面を粗面化処理するための方法として、例えば、
(1)硫酸を用いてエッチングを行う方法(特許文献1参照)、
(2)塩酸−リン酸系あるいは臭化水素酸系のエッチング液を用いてエッチングを行う方法(特許文献2参照)、
(3)酢酸−硫酸−塩酸−過酸化水素を用いたエッチング液、それを用いたエッチング方法(特許文献3参照)、
(4)リン酸−過酸化水素もしくは、これに塩酸を加えたエッチング液を用いたエッチング方法(特許文献4参照)、
などが提案されている。
Incidentally, in recent years, AlGaInP films have been used in high-intensity LEDs of yellow-green to red. And as a method for roughening the surface of this AlGaInP film (semiconductor film), for example,
(1) A method of etching using sulfuric acid (see Patent Document 1),
(2) A method of performing etching using a hydrochloric acid-phosphoric acid based or hydrobromic acid based etching solution (see Patent Document 2),
(3) Etching solution using acetic acid-sulfuric acid-hydrochloric acid-hydrogen peroxide, etching method using the same (see Patent Document 3),
(4) An etching method using phosphoric acid-hydrogen peroxide or an etching solution obtained by adding hydrochloric acid to the phosphoric acid-hydrogen peroxide (see Patent Document 4),
Etc. have been proposed.
しかしながら、上述の従来の方法では、AlGaInP膜を効率よく、所望の粗さで粗面化(凹凸化)するのは必ずしも容易ではないのが実情である。 However, in the conventional method described above, it is not always easy to efficiently roughen (roughen) the AlGaInP film with a desired roughness.
一方、AlGaInP膜の表面を凹凸化する技術として、ドライエッチングを用いる技術も提案されている。このドライエッチング方法としては、
(5)例えば、AlGaInP膜上にエッチングマスクを形成した後、ドライエッチングを行う方法や、自己組成化を利用したエッチングマスクを形成した後ドライエッチングする方法(特許文献5参照)、
(6)金属の凝集粒によってエッチングマスクを形成する方法(特許文献6参照)
などが提案されている。
On the other hand, a technique using dry etching has been proposed as a technique for making the surface of the AlGaInP film uneven. As this dry etching method,
(5) For example, a method of performing dry etching after forming an etching mask on an AlGaInP film, or a method of performing dry etching after forming an etching mask using self-composition (see Patent Document 5),
(6) Method of forming an etching mask with metal agglomerates (see Patent Document 6)
Etc. have been proposed.
しかしながら、上述のドライエッチング法では、エッチングマスクを形成する工程が必要で、かつ、エッチングマスクの形成工程に、特殊な技術を使用する必要があることから、工程が煩雑化して、スループットが低下し、コストの増大を招くという問題点がある。 However, the above-described dry etching method requires a process for forming an etching mask, and a special technique must be used for the etching mask forming process, which complicates the process and reduces the throughput. There is a problem that the cost increases.
本発明は、上記課題を解決するものであり、特殊な技術を用いることなく、LEDの光取り出し面を構成する半導体膜の表面を、効率よくエッチングして粗面化(凹凸化)することが可能なエッチング液組成物および該エッチング液組成物を用いたエッチング方法を提供することを目的とする。 The present invention solves the above-mentioned problems, and without using a special technique, the surface of the semiconductor film constituting the light extraction surface of the LED can be efficiently etched to be roughened (roughened). It is an object of the present invention to provide a possible etching solution composition and an etching method using the etching solution composition.
本発明者らは、上記課題を解決するために、エッチング液の組成について、鋭意検討を行い、特定の酸と、金属成分とを含むエッチング液を用いた場合に、光取り出し面となる半導体膜、特にAlGaInP膜を、低温かつ短時間で粗面化(凹凸化)できることを知り、さらに検討、実験を行って、本発明を完成するに至った。
すなわち、本発明のエッチング液組成物は、
AlGaInP膜の表面をエッチングすることにより、その表面を粗面化するために用いられるエッチング液組成物であって、
(a)無機酸と、
(b)金属化合物と、
(c)有機酸、有機酸塩、無機酸塩、界面活性剤からなる群より選ばれる少なくとも1種
を含むことを特徴としている。
In order to solve the above-mentioned problems, the present inventors have intensively studied the composition of an etching solution, and when an etching solution containing a specific acid and a metal component is used, a semiconductor film that becomes a light extraction surface In particular, it has been found that an AlGaInP film can be roughened (roughened) at a low temperature and in a short time, and further studies and experiments have been carried out to complete the present invention.
That is, the etching solution composition of the present invention is
An etching solution composition used to roughen the surface of an AlGaInP film by etching the surface,
(a) an inorganic acid;
(b) a metal compound;
(c) It includes at least one selected from the group consisting of organic acids, organic acid salts, inorganic acid salts, and surfactants .
また、前記無機酸は、塩酸、リン酸、硫酸、硝酸からなる群より選ばれる少なくとも1種であることが好ましい。 The inorganic acid is preferably at least one selected from the group consisting of hydrochloric acid, phosphoric acid, sulfuric acid, and nitric acid.
また、前記金属化合物として、鉄系化合物を含むことが好ましい。 Moreover, it is preferable that an iron-type compound is included as said metal compound.
また、前記鉄系化合物は、塩化鉄、硝酸鉄、硫酸鉄、リン酸鉄、酢酸鉄、乳酸鉄、クエン酸鉄からなる群より選ばれる少なくとも1種であることが好ましい。 The iron-based compound is preferably at least one selected from the group consisting of iron chloride, iron nitrate, iron sulfate, iron phosphate, iron acetate, iron lactate, and iron citrate.
また、前記有機酸および前記有機酸塩は、モノカルボン酸、ポリカルボン酸、オキシカルボン酸、ホスホン酸、スルホン酸およびその塩からなる群より選ばれる少なくとも1種であることが好ましい。 The organic acid and the organic acid salt are preferably at least one selected from the group consisting of monocarboxylic acids, polycarboxylic acids, oxycarboxylic acids, phosphonic acids, sulfonic acids and salts thereof.
また、前記有機酸は、酢酸であることが好ましい。 The organic acid is preferably acetic acid.
また、前記無機酸塩は、塩酸、リン酸、硫酸、硝酸の塩からなる群より選ばれる少なくとも1種であることが好ましい。 The inorganic acid salt is preferably at least one selected from the group consisting of salts of hydrochloric acid, phosphoric acid, sulfuric acid, and nitric acid.
また、前記界面活性剤は、両性界面活性剤、アニオン性界面活性剤、ノニオン性界面活性剤からなる群より選ばれる少なくとも1種であることが好ましい。 The surfactant is preferably at least one selected from the group consisting of amphoteric surfactants, anionic surfactants, and nonionic surfactants.
また、前記無機酸が塩酸であり、前記金属化合物が塩化鉄であり、前記有機酸が酢酸であることが好ましい。 Further, it is preferable that the inorganic acid is hydrochloric acid, the metal compound is iron chloride, and the organic acid is acetic acid.
また、本発明のエッチング方法は、本発明にかかるエッチング液組成物を用いてAlGaInP膜をエッチングし、表面を粗面化することを特徴としている。 The etching method of the present invention is characterized in that the AlGaInP film is etched using the etching solution composition according to the present invention to roughen the surface.
また、本発明のエッチング方法は、AlGaInP膜をエッチングし、表面を粗面化するためのエッチング方法であって、請求項1〜9のいずれかに記載のエッチング液組成物を用いてAlGaInP膜のエッチングを行う第1のエッチング工程と、前記第1のエッチング工程の終了後に、さらに、請求項1〜9のいずれかに記載のエッチング液組成物であって、前記第1のエッチング工程で用いたエッチング液組成物とは組成の異なるエッチング液組成物を用いて前記AlGaInP膜のエッチングを行う第2のエッチング工程とを備えていることを特徴としている。 The etching method of the present invention is an etching method for etching an AlGaInP film to roughen the surface , and using the etching solution composition according to any one of claims 1 to 9 , After the completion of the first etching step for performing etching and the first etching step, the etching solution composition according to any one of claims 1 to 9 , which is used in the first etching step. And a second etching step of etching the AlGaInP film using an etching solution composition having a composition different from that of the etching solution composition.
本発明のエッチング液組成物を、AlGaInP膜のエッチングに用いることにより、低温で、かつ短時間に、半導体膜を効率よくエッチングして、エッチング面に凹凸形状を形成することができる。さらに、組成の選択により、凹凸の形状、凹凸の大きさ、エッチング量などをコントロールすることが可能になる。したがって、エッチングプロセスにあった組成を適切に選択することにより、効率よく、エッチングを行って、上述の半導体膜の表面を、意図するような凹凸を有する所望の状態とすることができる。 By using the etching solution composition of the present invention for etching an AlGaInP film , the semiconductor film can be efficiently etched at a low temperature and in a short time to form an uneven shape on the etched surface. Furthermore, the shape of the unevenness, the size of the unevenness, the etching amount, etc. can be controlled by selecting the composition. Therefore, by appropriately selecting a composition suitable for the etching process, the etching can be efficiently performed so that the surface of the above-described semiconductor film has a desired state having unevenness as intended.
以下、本発明のエッチング液およびエッチング方法について、詳細に説明する。
本発明のエッチング液組成物は、無機酸と、金属化合物とを含む。そして、本発明のエッチング液組成物に用いることが可能な無機酸としては、例えば、塩酸、リン酸、硫酸、硝酸などが挙げられ、特に好ましくは塩酸とリン酸が挙げられる。
Hereinafter, the etching solution and the etching method of the present invention will be described in detail.
The etching solution composition of the present invention contains an inorganic acid and a metal compound. And as an inorganic acid which can be used for the etching liquid composition of this invention, hydrochloric acid, phosphoric acid, a sulfuric acid, nitric acid etc. are mentioned, for example, Especially preferably, hydrochloric acid and phosphoric acid are mentioned.
無機酸の濃度は、実用上、所望のエッチング形状が得られればよく、AlGaInP膜の組成を考慮して決定することが好ましい。例えば、塩酸の場合、濃度は1〜30重量%の範囲とすることが好ましく、10〜22重量%の範囲とすることがより好ましい。また、リン酸の場合、濃度は1〜75重量%の範囲とすることが好ましく、40〜70重量%の範囲とすることがより好ましい。
なお、これらの無機酸としては、1種類の無機酸を単独で用いてもよく、また、2種以上の無機酸を組み合わせて用いてもよい。
The concentration of the inorganic acid may be practically determined as long as a desired etching shape is obtained, and is preferably determined in consideration of the composition of the AlGaInP film. For example, in the case of hydrochloric acid, the concentration is preferably in the range of 1 to 30% by weight, and more preferably in the range of 10 to 22% by weight. In the case of phosphoric acid, the concentration is preferably in the range of 1 to 75% by weight, and more preferably in the range of 40 to 70% by weight.
In addition, as these inorganic acids, one type of inorganic acid may be used alone, or two or more types of inorganic acids may be used in combination.
本発明のエッチング液組成物に用いることが可能な金属化合物としては、鉄系化合物が挙げられる。鉄系化合物としては、塩化鉄、硫酸鉄、硝酸鉄、リン酸鉄、酢酸鉄、乳酸鉄、クエン酸鉄などが挙げられる、その中でも好ましいのは、塩化鉄と硫酸鉄である。鉄系化合物濃度は、実用上所望のエッチング形状が得られればよく、AlGaInP膜の組成を考慮して適宜決定することができる。塩化鉄の場合、0.1〜20重量%の範囲とすることが好ましく、1〜15重量%の範囲とすることがより好ましい。硫酸鉄の場合、0.1〜30重量%の範囲とすることが好ましく、1〜20重量%の範囲とすることがより好ましい。
なお、これらの金属化合物は、単独で用いてもよく、また、2種以上を組み合わせて用いてもよい。
Examples of the metal compound that can be used in the etching solution composition of the present invention include iron-based compounds. Examples of the iron-based compound include iron chloride, iron sulfate, iron nitrate, iron phosphate, iron acetate, iron lactate, and iron citrate. Among them, iron chloride and iron sulfate are preferable. The iron-based compound concentration may be determined as appropriate in consideration of the composition of the AlGaInP film as long as a practically desired etching shape can be obtained. In the case of iron chloride, the content is preferably in the range of 0.1 to 20% by weight, and more preferably in the range of 1 to 15% by weight. In the case of iron sulfate, the range is preferably 0.1 to 30% by weight, and more preferably 1 to 20% by weight.
In addition, these metal compounds may be used independently and may be used in combination of 2 or more type.
また、本発明のエッチング液組成物に用いることが可能な有機酸、および有機酸塩としては、モノカルボン酸、ポリカルボン酸、オキシカルボン酸、ホスホン酸、スルホン酸およびその塩が挙げられる。 Examples of the organic acid and organic acid salt that can be used in the etching solution composition of the present invention include monocarboxylic acid, polycarboxylic acid, oxycarboxylic acid, phosphonic acid, sulfonic acid, and salts thereof.
有機酸および有機酸塩としては、具体的には、ギ酸、酢酸、プロピオン酸などのモノカルボン酸、シュウ酸、マロン酸、コハク酸、グルタル酸などのポリカルボン酸、グリコール酸、乳酸、リンゴ酸、酒石酸、クエン酸などのオキシカルボン酸、アミノトリ(メチレンホスホン酸)、1−ヒドロキシエチリデン−1,1−ジホスホン酸などのホスホン酸、メタンスルホン酸、エタンスルホン酸などのスルホン酸またはその塩などが挙げられる。 Specific examples of organic acids and organic acid salts include monocarboxylic acids such as formic acid, acetic acid and propionic acid, polycarboxylic acids such as oxalic acid, malonic acid, succinic acid and glutaric acid, glycolic acid, lactic acid and malic acid. Oxycarboxylic acids such as tartaric acid and citric acid, phosphonic acids such as aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, sulfonic acids such as methanesulfonic acid and ethanesulfonic acid, or salts thereof Can be mentioned.
また、有機酸塩としては、上述の有機酸のアンモニウム塩、モノエタノールアミン、トリエタノールアミンなどの有機アミン塩、テトラメチルアンモニウム水酸化物、テトラエチルアンモニウム水酸化物などの四級アンモニウム塩、ナトリウム、カリウムなどのアルカリ金属塩などが挙げられる。 Moreover, as organic acid salt, ammonium salt of the above-mentioned organic acid, organic amine salt such as monoethanolamine and triethanolamine, quaternary ammonium salt such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, sodium, Examples thereof include alkali metal salts such as potassium.
有機酸および有機酸塩の中で、特に好ましいものとして、酢酸および酢酸塩が挙げられる。また、有機酸として酢酸を用いる場合、その濃度は1〜70重量%の範囲とすることが好ましく、10〜40重量%の範囲とすることがより好ましい。
なお、これらの有機酸および有機酸塩は、単独で用いてもよく、また、2種以上を組み合わせて用いてもよい。
Among organic acids and organic acid salts, acetic acid and acetate are particularly preferable. Moreover, when using acetic acid as an organic acid, it is preferable to make the density | concentration into the range of 1-70 weight%, and it is more preferable to set it as the range of 10-40 weight%.
These organic acids and organic acid salts may be used alone or in combination of two or more.
また、本発明のエッチング液組成物に用いることが可能な界面活性剤としては、両性界面活性剤、アニオン性界面活性剤、ノニオン性界面活性剤が挙げられる。 Examples of surfactants that can be used in the etching solution composition of the present invention include amphoteric surfactants, anionic surfactants, and nonionic surfactants.
両性界面活性剤としては、具体的には、パーフルオロアミンオキシド系、パーフルオロアルキルベタイン系、アルキルアミンオキシド系、アルキルベタイン系などが挙げられる。 Specific examples of amphoteric surfactants include perfluoroamine oxides, perfluoroalkylbetaines, alkylamine oxides, alkylbetaines, and the like.
アニオン性界面活性剤としては、パーフルオロアルキルスルホン酸およびその塩、アルキルスルホン酸およびその塩などが挙げられる。
ノニオン性界面活性剤としては、パーフルオロアルキルアミンオキシド、ポリオキシエチレンアルキルエーテルなどが挙げられる。
Examples of the anionic surfactant include perfluoroalkyl sulfonic acid and its salt, alkyl sulfonic acid and its salt, and the like.
Examples of nonionic surfactants include perfluoroalkylamine oxide and polyoxyethylene alkyl ether.
界面活性剤の中では、両性界面活性剤が特に好ましく用いられる。この両性界面活性剤の濃度の好ましい範囲は、0.001〜1重量%の範囲であり、より好ましくは、0.005〜0.1重量%の範囲である。 Among the surfactants, amphoteric surfactants are particularly preferably used. A preferable range of the concentration of the amphoteric surfactant is 0.001 to 1% by weight, and more preferably 0.005 to 0.1% by weight.
なお、本発明のエッチング液組成物は、通常、水溶液として用いられるが、場合によっては有機溶剤を共存させることも可能である。
また、本発明のエッチング液組成物は、さらに他の添加剤を共存させることも可能である。
In addition, although the etching liquid composition of this invention is normally used as aqueous solution, depending on the case, an organic solvent can also coexist.
In addition, the etching solution composition of the present invention can further coexist with other additives.
本発明のエッチング液組成物は、レジストにダメージを与えることが少なく、レジストマスクを施した状態でエッチングに使用することが可能であり、精度の高いエッチングパターンを得ることができる。 The etching solution composition of the present invention hardly damages the resist, can be used for etching in a state where a resist mask is applied, and a highly accurate etching pattern can be obtained.
また、本発明のエッチング液組成物は、室温で使用して、十分なエッチング効果を得ることが可能であるが、用途に応じて加熱して使用することも可能である。すなわち、使用温度などの条件を適切に選択することにより、所望のエッチング速度およびエッチング時間を得ることができる。 Moreover, although the etching liquid composition of this invention can be used at room temperature and can acquire sufficient etching effect, it can also be heated and used according to a use. That is, a desired etching rate and etching time can be obtained by appropriately selecting conditions such as operating temperature.
また、本発明のエッチング液組成物を用いた、半導体膜であるAlGaInP膜のエッチング方法としては、例えば、AlGaInP膜が形成された基板をエッチング液に直接浸漬し、基板自体を静止、揺動あるいはエッチング液を撹拌する、いわゆるディッピングによる方法や、スプレーノズルよりエッチング液を基板上に供給するスプレー処理による方法などが挙げられる。 Moreover, as an etching method of the AlGaInP film, which is a semiconductor film, using the etching solution composition of the present invention, for example, the substrate on which the AlGaInP film is formed is directly immersed in the etching solution, and the substrate itself is stationary, swung, or Examples include a so-called dipping method in which the etching solution is stirred, and a spraying method in which the etching solution is supplied onto the substrate from a spray nozzle.
また、本発明のエッチング液組成物は、半導体膜の表面をエッチングすることにより、半導体膜の表面に凹凸を形成する(粗面化する)のに好適に用いられるものであり、本発明のエッチング液組成物を用いて効率よく、所望のエッチングを行うことが可能な半導体膜としては、AlGaInP膜、AlGaAs膜、GaAsP膜、GaInP膜、AlGaP膜、AlInP膜、GaP膜などを挙げることができる。その中でも、特にAlGaInP膜をエッチングするのに好適に用いることができる。 Further, the etching solution composition of the present invention is suitably used for forming irregularities (roughening) on the surface of the semiconductor film by etching the surface of the semiconductor film. Examples of the semiconductor film that can be efficiently etched using the liquid composition include an AlGaInP film, an AlGaAs film, a GaAsP film, a GaInP film, an AlGaP film, an AlInP film, and a GaP film. Among them, it can be suitably used particularly for etching an AlGaInP film.
また、本発明のエッチング液組成物を用いてエッチングを行うにあたっては、所定の組成のエッチング液組成物を用いてエッチングを実施するようにしてもよいが、異なる組成のエッチング液組成物を用いてエッチングを施すことも可能である。
すなわち、本発明のエッチング液組成物を用いてエッチングを行うにあたっては、所定のエッチング液組成物を用いて第1のエッチング工程を実施し、その後、第1のエッチング工程で用いたエッチング液組成物とは組成の異なるエッチング液組成物を用いて第2のエッチング工程を実施するようにしてもよい。
このように、異なる組成のエッチング液組成物を用いてエッチングを施すことにより、半導体膜の表面を、意図するような凹凸を有する所望の状態とすることができる。
Further, in performing etching using the etching solution composition of the present invention, etching may be performed using an etching solution composition having a predetermined composition, but an etching solution composition having a different composition may be used. It is also possible to perform etching.
That is, in performing etching using the etching solution composition of the present invention, the first etching step is performed using a predetermined etching solution composition, and then the etching solution composition used in the first etching step. You may make it implement a 2nd etching process using the etching liquid composition from which a composition differs.
As described above, by performing etching using the etching solution compositions having different compositions, the surface of the semiconductor film can be brought into a desired state having unevenness as intended.
以下に実施例によって本発明をより具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
[エッチング液組成物(試料)の作製]
塩酸、リン酸、酢酸、乳酸、硫酸、過酸化水素(H2O2)、塩化鉄、硫酸鉄、硝酸鉄、パーフルオロアルキルアミンオキシド(両性界面活性剤)、パーフルオロアルキルスルホン酸(アニオン性界面活性剤)などの原料を用意した。
これらの原料を、表1に示すような組成となるように秤取し、水に溶解することにより表1の試料番号1〜15の各試料(エッチング液組成物)を作製した。
なお、試料番号2〜10の試料は本発明の要件を備えた実施例の試料であり、試料番号1は参考例の試料、試料番号11〜15の試料は本発明の要件を備えていない比較例の試料である。
[Production of Etching Solution Composition (Sample)]
Hydrochloric acid, phosphoric acid, acetic acid, lactic acid, sulfuric acid, hydrogen peroxide (H 2 O 2 ), iron chloride, iron sulfate, iron nitrate, perfluoroalkylamine oxide (amphoteric surfactant), perfluoroalkylsulfonic acid (anionic) Raw materials such as surfactants were prepared.
These raw materials were weighed so as to have a composition as shown in Table 1, and dissolved in water to prepare samples (etching liquid compositions) of sample numbers 1 to 15 in Table 1.
Samples Nos. 2 to 10 are samples of the examples having the requirements of the present invention, Sample No. 1 is a sample of the reference example, and Samples of Sample Nos. 11 to 15 are comparisons not having the requirements of the present invention. Example sample.
[評価試験]
(1)表面に半導体膜が形成された評価用の基板
上述のようにして作製したエッチング液組成物の性能を評価するにあたって、表面に半導体膜が形成された基板を用いた。
この実施例では、GaAs基板上に膜厚が2μmのAlGaInP膜が成膜された基板を用いた。
[Evaluation test]
(1) Evaluation Substrate with Semiconductor Film Formed on the Surface In evaluating the performance of the etching solution composition produced as described above, a substrate with a semiconductor film formed on the surface was used.
In this example, a substrate in which an AlGaInP film having a thickness of 2 μm was formed on a GaAs substrate was used.
(2)評価方法
上述のようにして作製した各エッチング液に、膜厚が2μmのAlGaInP膜が表面に形成されたGaAs基板を25℃、5分間の条件で浸漬した。
その後、GaAs基板をエッチング液中から取り出し、水洗、乾燥を行った後、電子顕微鏡にて観察し、AlGaInP膜の表面状態を調べるとともに、凹凸の大きさ、エッチング量、レジストがダメージを受けているかどうかを調べた。その結果を表1に併せて示す。
(2) Evaluation Method A GaAs substrate on which a 2 μm thick AlGaInP film was formed was immersed in each etching solution prepared as described above at 25 ° C. for 5 minutes.
Thereafter, the GaAs substrate is taken out of the etching solution, washed with water, dried, and then observed with an electron microscope to examine the surface state of the AlGaInP film, and the size of the unevenness, etching amount, and whether the resist is damaged. I checked. The results are also shown in Table 1.
なお、AlGaInP膜の表面状態は、エッチングされた面に形成された凹凸の大きさの状態を示す概念であり、表1において、◎Aとして表示したものは、表面に比較的大きな凹凸があり、主に結晶方位に沿ってエッチングされることにより得られるような表面状態となっていることを表している(図1参照)。また、表1において、◎Bとして表示したものは、表面に比較的小さな凹凸があり、主として結晶方位によらずにエッチングされることにより得られるような表面状態となっていることを表している(図2参照)。
なお、光の反射を抑えて光取り出し効率を改善する見地からは、通常は、表面にある程度以上の大きさの凹凸が形成されている方が好ましいが、小さい凹凸が形成されている場合にも、光取り出し効率の改善効果がある場合もあり、必ずしも凹凸が大きければよいというものではない。
The surface state of the AlGaInP film is a concept indicating the state of the size of the unevenness formed on the etched surface. In Table 1, those indicated as 表示 A have relatively large unevenness on the surface, It represents that the surface state is obtained mainly by etching along the crystal orientation (see FIG. 1). Moreover, in Table 1, what is indicated as ◎ B indicates that there are relatively small irregularities on the surface, and the surface state is obtained mainly by etching regardless of the crystal orientation. (See FIG. 2).
From the standpoint of improving light extraction efficiency by suppressing light reflection, it is usually better to have irregularities with a certain size or more on the surface, but even when small irregularities are formed In some cases, the light extraction efficiency may be improved, and it is not always necessary that the unevenness is large.
また、表1における凹凸の大きさは、エッチング後のAlGaInP膜の、凹凸が形成された領域(エッチングされた領域)における、凸部の頂部から凹部の底部までの距離を、電子顕微鏡を用いて測定した値であり、表1では、複数箇所で測定した凹凸の大きさを、幅を持った値で示している。 The size of the unevenness in Table 1 is the distance from the top of the convex part to the bottom of the concave part in the region (etched region) where the unevenness was formed in the AlGaInP film after etching using an electron microscope. Table 1 shows the size of the unevenness measured at a plurality of locations as a value having a width.
なお、通常、結晶方位に沿ってエッチングされる程度が大きい場合には大きな凹凸が形成され、結晶方位によらずエッチングされる程度が大きい場合には、小さな凹凸が形成される傾向がある。 Normally, large unevenness is formed when the degree of etching along the crystal orientation is large, and small unevenness tends to be formed when the degree of etching is large regardless of the crystal orientation.
なお、上述の表面状態と、凹凸の大きさとは、AlGaInP膜の光の全反射を抑えて光取り出し効率を向上させる機能に大きな影響を与えるが、半導体膜の表面状態や凹凸の大きさをどのように制御するかは、半導体膜の種類などを考慮して決定されることになる。 Note that the above-described surface state and the size of the unevenness greatly affect the function of improving the light extraction efficiency by suppressing the total reflection of light of the AlGaInP film. The control is determined in consideration of the type of the semiconductor film.
また、表1におけるエッチング量(深さ)は、エッチング処理前とエッチング処理後の半導体膜の膜厚を、電子顕微鏡を用いて測定した場合における、エッチング処理前とエッチング処理後の膜厚の差である。なお、エッチング処理後にエッチング面に凹凸がある場合には、凹凸を平均して求めた膜厚を用いて、エッチング処理前後の膜厚の差を求め、エッチング量とした。 Moreover, the etching amount (depth) in Table 1 is the difference between the film thickness before and after the etching process when the film thickness of the semiconductor film before and after the etching process is measured using an electron microscope. It is. In the case where the etched surface has irregularities after the etching process, the difference in film thickness before and after the etching process was obtained using the film thickness obtained by averaging the irregularities, and was used as the etching amount.
また、レジストダメージの有無を確認するため、GaAs基板上に、例えば ポジ型のレジストを塗布、露光、現像して、レジスト膜を形成した。 In order to confirm the presence or absence of resist damage, for example, a positive resist was applied, exposed and developed on a GaAs substrate to form a resist film.
そして、レジスト膜を形成したGaAs基板を、試料番号1〜15の各エッチング液に、25℃、5分間の条件で浸漬した後、レジスト膜を観察してダメージの有無を調べた。その結果を表1に併せて示す。 And after immersing the GaAs substrate in which the resist film was formed in each etching liquid of sample numbers 1-15 on 25 degreeC and the conditions for 5 minutes, the resist film was observed and the presence or absence of damage was investigated. The results are also shown in Table 1.
(3)評価結果
表1に示すように、試料番号11〜15の、本発明の要件を備えていない比較例の試料(エッチング液組成物)を用いてエッチングを行った場合、AlGaInP膜に凹凸は形成されず、光の反射を抑えて光取り出し効率を向上させることができるような粗面化を行うことはできなかった。
(3) Evaluation results As shown in Table 1, when etching was performed using samples (etching liquid compositions) of sample numbers 11 to 15 that do not have the requirements of the present invention, the AlGaInP film was uneven. Thus, it was impossible to roughen the surface so as to suppress light reflection and improve the light extraction efficiency.
これに対し、試料番号1の参考例のエッチング液組成物、および、試料番号2〜10の、本発明の要件を備えたエッチング液組成物を用いてエッチングを行った場合、AlGaInP膜に、表1に示すような態様で効率よく凹凸を形成することができた。 On the other hand, when etching is performed using the etching solution composition of the reference example of sample number 1 and the etching solution composition of sample numbers 2 to 10 having the requirements of the present invention, the AlGaInP film is exposed to the surface. As a result, it was possible to efficiently form irregularities in the manner shown in FIG.
また、試料番号2〜10についての結果から、本発明の要件を備えた組成を有するエッチング液組成物の場合、組成を適切に選択することにより、表面状態や、凹凸の大きさ、エッチング量などをコントロールすることが可能で、半導体膜を効率よく、意図するような状態となるように、エッチングできることがわかる。 In the case of an etching solution composition having a composition having the requirements of the present invention based on the results of sample numbers 2 to 10, the surface state, the size of the unevenness, the etching amount, etc. can be selected by appropriately selecting the composition. It can be seen that the semiconductor film can be etched efficiently and in a desired state.
また、レジスト膜のダメージに関しては、試料番号15の比較例のエッチング液を用いた場合、レジスト膜がダメージを受けることが確認された。
一方、試料番号1の参考例のエッチング液組成物、および、試料番号2〜10の本発明の実施例にかかるエッチング液の場合、レジスト膜にダメージをあたえないことが確認された。
Regarding the damage to the resist film, it was confirmed that the resist film was damaged when the etching solution of Comparative Example No. 15 was used.
On the other hand, it was confirmed that the resist film was not damaged in the case of the etching solution composition of the reference example of sample number 1 and the etching solutions according to the examples of the present invention of sample numbers 2 to 10.
なお、この実施例では、半導体膜としてAlGaInP膜をエッチングする場合について説明したが、本発明は、半導体膜がAlGaAs膜、GaAsP膜、GaInP膜、AlGaP膜、AlInP膜、GaP膜である場合にも同様の作用効果を奏することが確認されている。 In this embodiment, the case where the AlGaInP film is etched as the semiconductor film has been described. However, the present invention also applies to the case where the semiconductor film is an AlGaAs film, a GaAsP film, a GaInP film, an AlGaP film, an AlInP film, or a GaP film. It has been confirmed that similar effects can be achieved.
また、この実施例では、いずれか1種のエッチング液を用いてエッチングを行ったが、本発明のエッチング液組成物を用いてエッチングを行うにあたっては、所定のエッチング液組成物を用いて第1のエッチング工程を実施し、その後、第1のエッチング工程で用いたエッチング液組成物とは組成の異なるエッチング液組成物を用いて第2のエッチング工程を実施することも可能である。その場合、さらによく、表面状態や、凹凸の大きさ、エッチング量などをコントロールして、意図するような凹凸を有する所望の表面状態の半導体膜を得ることができる。 In this example, etching was performed using any one type of etching solution. However, when etching is performed using the etching solution composition of the present invention, first etching is performed using a predetermined etching solution composition. It is also possible to perform the second etching step using an etching solution composition having a composition different from that of the etching solution composition used in the first etching step. In that case, a semiconductor film having a desired surface state having the intended unevenness can be obtained by better controlling the surface state, the size of the unevenness, the etching amount, and the like.
本発明は、さらにその他の点においても上記実施例に限定されるものではなく、本発明の範囲内において、種々の応用、変形を加えることが可能である。 The present invention is not limited to the above-described embodiment in other points, and various applications and modifications can be made within the scope of the present invention.
本発明のエッチング液組成物を用いて、AlGaInP膜をエッチングすることにより、低温かつ短時間で、半導体膜の表面に所望の凹凸を形成することが可能になり、これまでのLEDの製造工程を簡略化して、スループットの向上とコストの低減を図ることができる。したがって、本発明のエッチング液組成物およびそれを用いたエッチング方法は、LED製造技術分野において広く利用することが可能である。 By etching the AlGaInP film using the etching solution composition of the present invention, it becomes possible to form desired irregularities on the surface of the semiconductor film at a low temperature and in a short time. Simplification can improve throughput and reduce costs. Therefore, the etching solution composition of the present invention and the etching method using the same can be widely used in the LED manufacturing technical field.
Claims (11)
(a)無機酸と、
(b)金属化合物と、
(c)有機酸、有機酸塩、無機酸塩、界面活性剤からなる群より選ばれる少なくとも1種
を含むことを特徴とするエッチング液組成物。 An etching solution composition used to roughen the surface of an AlGaInP film by etching the surface,
(a) an inorganic acid;
(b) a metal compound;
(c) An etching solution composition comprising at least one selected from the group consisting of organic acids, organic acid salts, inorganic acid salts, and surfactants .
請求項1〜9のいずれかに記載のエッチング液組成物を用いてAlGaInP膜のエッチングを行う第1のエッチング工程と、
前記第1のエッチング工程の終了後に、さらに、請求項1〜9のいずれかに記載のエッチング液組成物であって、前記第1のエッチング工程で用いたエッチング液組成物とは組成の異なるエッチング液組成物を用いて前記AlGaInP膜のエッチングを行う第2のエッチング工程と
を備えていることを特徴とするエッチング方法。 An etching method for etching an AlGaInP film to roughen the surface,
A first etching step of etching the AlGaInP layer using an etching solution composition according to any one of claims 1 to 9,
After the completion of the first etching step, the etching solution composition according to any one of claims 1 to 9 , wherein the etching solution composition is different from the etching solution composition used in the first etching step. And a second etching step of etching the AlGaInP film using a liquid composition.
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