TWI547546B - Etching liquid composition and etching method - Google Patents
Etching liquid composition and etching method Download PDFInfo
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- TWI547546B TWI547546B TW100135007A TW100135007A TWI547546B TW I547546 B TWI547546 B TW I547546B TW 100135007 A TW100135007 A TW 100135007A TW 100135007 A TW100135007 A TW 100135007A TW I547546 B TWI547546 B TW I547546B
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- etching
- acid
- liquid composition
- etching liquid
- film
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- 238000005530 etching Methods 0.000 title claims description 162
- 239000000203 mixture Substances 0.000 title claims description 77
- 239000007788 liquid Substances 0.000 title claims description 72
- 238000000034 method Methods 0.000 title claims description 35
- 239000004065 semiconductor Substances 0.000 claims description 35
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- -1 organic acid salts Chemical class 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- 150000007524 organic acids Chemical class 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 150000002736 metal compounds Chemical class 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 150000007522 mineralic acids Chemical class 0.000 claims description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 239000002280 amphoteric surfactant Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 7
- 239000003945 anionic surfactant Substances 0.000 claims description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 235000005985 organic acids Nutrition 0.000 claims description 6
- 229910000980 Aluminium gallium arsenide Inorganic materials 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 238000007788 roughening Methods 0.000 claims description 5
- 229910052500 inorganic mineral Inorganic materials 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
- 239000011707 mineral Substances 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
- GOKIPOOTKLLKDI-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O.CC(O)=O GOKIPOOTKLLKDI-UHFFFAOYSA-N 0.000 claims description 3
- 150000007513 acids Chemical class 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
- 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
- 229960002413 ferric citrate Drugs 0.000 claims description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 150000002506 iron compounds Chemical class 0.000 claims 1
- 150000003009 phosphonic acids Chemical class 0.000 claims 1
- 150000003460 sulfonic acids Chemical class 0.000 claims 1
- 239000000758 substrate Substances 0.000 description 11
- 229920002120 photoresistant polymer Polymers 0.000 description 9
- 235000011054 acetic acid Nutrition 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 5
- 238000001312 dry etching Methods 0.000 description 5
- 230000000694 effects Effects 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
- 238000004519 manufacturing process Methods 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 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
- 230000000052 comparative effect Effects 0.000 description 3
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-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
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 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
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 2
- 239000002994 raw material Substances 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
- 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
- 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
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-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
- 239000007983 Tris buffer Substances 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
- 150000001412 amines Chemical class 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
- 239000007864 aqueous solution Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- JLLMDXDAVKMMEG-UHFFFAOYSA-N hydrogen peroxide phosphoric acid Chemical compound OO.OP(O)(O)=O JLLMDXDAVKMMEG-UHFFFAOYSA-N 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 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
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000002245 particle Substances 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
- 238000012552 review Methods 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
- 238000003756 stirring Methods 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 compound [O-][N+](F)(F)F UDOZVPVDQKQJAP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- H01L33/005—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
- 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
Landscapes
- Engineering & Computer Science (AREA)
- 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
本發明係有關一種蝕刻組成物及使用它之之蝕刻方法，詳言之，係有關為使發光二極管(以下稱為「LED」)之採光面等所使用的半導體膜予以蝕刻時之蝕刻液及使用它之蝕刻方法。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 lighting surface of a light emitting diode (hereinafter referred to as "LED") Use its etching method.
一般而言，LED被要求高的發光效率。其次，LED之發光效率係藉由內部量子效率與採光效率之積予以決定。因此，提高發光效率時，必須增加該數值。In general, LEDs are required to have high luminous efficiency. Second, the luminous efficiency of LEDs is determined by the product of internal quantum efficiency and lighting efficiency. Therefore, when the luminous efficiency is improved, the value must be increased.
其中，提高採光效率之技術，提案有進行在採光面之半導體膜的表面上形成凹凸的加工(粗面化處理)，抑制光反射予以提高的方法。Among them, a technique for improving the light-receiving efficiency has been proposed to perform a process of forming irregularities on the surface of a semiconductor film on a lighting surface (roughening treatment), and to suppress improvement of light reflection.
近年來，於黃綠色～紅色之高亮度LED中，利用AlGaInP膜。其次，使該AlGaInP膜(半導體膜)之表面進行粗面化處理的方法，例如提案有In recent years, AlGaInP films have been used in high-brightness LEDs of yellow-green to red. Next, a method of roughening the surface of the AlGaInP film (semiconductor film) is proposed, for example.
(1) 使用硫酸進行蝕刻的方法(參照專利文獻1)，(1) A method of etching using sulfuric acid (refer to Patent Document 1),
(2) 使用鹽酸-磷酸系或溴化氫酸系之蝕刻液進行蝕刻的方法(參照專利文獻2)，(2) A method of etching using a hydrochloric acid-phosphoric acid or a hydrogen bromide-based etching solution (see Patent Document 2),
(3) 使用醋酸-硫酸-鹽酸-過氧化氫之蝕刻液，使用它之蝕刻方法(參照專利文獻3)，(3) An etching method using acetic acid-sulfuric acid-hydrochloric acid-hydrogen peroxide, using the etching method thereof (refer to Patent Document 3),
(4) 使用磷酸-過氧化氫或於其中加入鹽酸之蝕刻液進行蝕刻的方法(參照專利文獻4)等。(4) A method of etching using phosphoric acid-hydrogen peroxide or an etching solution to which hydrochloric acid is added (see Patent Document 4).
然而，上述之習知方法，實際上必須有效地、以企求的粗糙度使AlGaInP膜粗面化(凹凸化)不為容易。However, in the above-described conventional method, it is actually not necessary to effectively roughen (concave and roughen) the AlGaInP film with a desired roughness.
另外，使AlGaInP膜之表面凹凸化的技術，亦提案有使用乾式蝕刻的技術。該乾式蝕刻方法提案有Further, a technique of using a dry etching is also proposed as a technique for making the surface of the AlGaInP film rough. The dry etching method proposal has
(5) 例如在AlGaInP膜上形成蝕刻光罩後，進行乾式蝕刻的方法，或形成利用自己組成化的蝕刻光罩後，進行乾式蝕刻的方法(參照專利文獻5)，(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 by forming an etching mask of its own composition (refer to Patent Document 5),
(6) 藉由金屬之凝聚粒子以形成蝕刻光罩的方法(參照專利文獻6)等。(6) A method of forming an etching mask by agglomerating particles of metal (see Patent Document 6).
然而，上述之乾式蝕刻法，必須有形成蝕刻光罩的步驟，且由於在形成蝕刻光罩的步驟中必須使用特殊的技術，會有步驟繁雜化，導致供應量降低且成本增加的問題。However, in the above dry etching method, it is necessary to have a step of forming an etching mask, and since a special technique must be used in the step of forming the etching mask, there are problems that the steps are complicated, resulting in a decrease in supply amount and an increase in cost.
[專利文獻1]日本特開平5-326485號[Patent Document 1] Japanese Patent Laid-Open No. 5-326485
[專利文獻2]日本特開平2-260636號[Patent Document 2] Japanese Patent Laid-Open No. 2-260636
[專利文獻3]日本特開2001-267307號[Patent Document 3] Japanese Patent Laid-Open No. 2001-267307
[專利文獻4]日本特開2007-194536號[Patent Document 4] Japanese Patent Laid-Open No. 2007-194536
[專利文獻5]日本特開2006-108635號[Patent Document 5] Japanese Patent Laid-Open No. 2006-108635
[專利文獻6]日本特開2007-59518號[Patent Document 6] Japanese Patent Laid-Open No. 2007-59518
本發明係為解決上述課題者，以提供一種不需使用特殊技術，可有效地蝕刻構成LED之採光面的半導體膜表面，予以粗面化(凹凸化)的蝕刻液組成物及使用該蝕刻液組成物之蝕刻方法為目的。In order to solve the above problems, the present invention provides an etching liquid composition which can effectively etch a surface of a semiconductor film which constitutes a lighting surface of an LED without using a special technique, and which is roughened (concavo-convex) and uses the etching liquid. The etching method of the composition is for the purpose.
本發明人等為解決上述課題時，有關蝕刻液之組成，再三深入研究檢討的結果，使用含有特定酸與金屬成分之蝕刻液時，已知可使採光面之半導體膜、特別是AlGaInP膜在低溫且短時間內進行粗面化(凹凸化)，另外再進行檢討、實驗，遂而完成本發明。In order to solve the above-mentioned problems, the inventors of the present invention have studied the composition of the etching liquid, and have repeatedly studied the results of the review. When an etching solution containing a specific acid and a metal component is used, it is known that the semiconductor film of the lighting surface, particularly the AlGaInP film, can be The present invention was completed by performing roughening (concavity reduction) at a low temperature and in a short period of time, and further reviewing and experimenting.
換言之，本發明之蝕刻液組成物，其係藉由蝕刻半導體膜之表面，用以使其表面粗面化時所使用的蝕刻液，其特徵為含有In other words, the etching liquid composition of the present invention is characterized in that the etching liquid used for etching the surface of the semiconductor film to roughen the surface thereof is characterized by containing
(a) 無機酸、與(a) inorganic acids, and
(b) 金屬化合物。(b) Metal compounds.
本發明之蝕刻液，其特徵為進一步含有(c)選自由有機酸、有機酸鹽、無機酸鹽、界面活性劑所成群之至少1種。The etching solution of the present invention is characterized by further comprising (c) at least one selected from the group consisting of organic acids, organic acid salts, inorganic acid salts, and surfactants.
此外，前述無機酸以選自由鹽酸、磷酸、硫酸、硝酸所成群之至少1種較佳。Further, the inorganic acid is preferably at least one selected from the group consisting of hydrochloric acid, phosphoric acid, sulfuric acid, and nitric acid.
另外，前述金屬化合物以含有鐵系化合物較佳。Further, the metal compound is preferably an iron-based compound.
而且，前述鐵系化合物以選自由氯化鐵、硝酸鐵、硫酸鐵、磷酸鐵、醋酸鐵、乳酸鐵、檸檬酸鐵所成群之至少1種較佳。Further, the iron-based compound is preferably at least one selected from the group consisting of ferric chloride, iron nitrate, iron sulfate, iron phosphate, iron acetate, iron lactate, and ferric citrate.
此外，前述有機酸及前述有機酸鹽以選自由單羧酸、聚羧酸、氧化羧酸、膦酸、磺酸及其鹽所成群之至少1種較佳。Further, the organic acid and the organic acid salt are preferably at least one selected from the group consisting of a monocarboxylic acid, a polycarboxylic acid, an oxidized carboxylic acid, a phosphonic acid, a sulfonic acid, and a salt thereof.
另外，前述有機酸以醋酸較佳。Further, the above organic acid is preferably acetic acid.
而且，前述無機酸鹽以選自由鹽酸、磷酸、硫酸、硝酸之鹽所成群之至少1種較佳。Further, 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.
此外，前述界面活性劑以選自由兩性界面活性劑、陰離子性界面活性劑、非離子性界面活性劑所成群之至少1種較佳。Further, the surfactant is preferably at least one selected from the group consisting of an amphoteric surfactant, an anionic surfactant, and a nonionic surfactant.
另外，以前述無機酸為鹽酸，前述金屬化合物為氯化鐵，前述有機酸為醋酸較佳。Further, the inorganic acid is hydrochloric acid, the metal compound is ferric chloride, and the organic acid is preferably acetic acid.
而且，本發明之蝕刻液組成物，其特徵為蝕刻選自由AlGaInP膜、AlGaAs膜、GaAsP膜所成群之任一種的半導體膜時所使用者。Further, the etching liquid composition of the present invention is characterized in that the semiconductor film selected from the group consisting of an AlGaInP film, an AlGaAs film, and a GaAsP film is etched.
此外，本發明之蝕刻方法，其特徵為使用本發明之蝕刻液組成物來進行蝕刻半導體膜，且使表面粗面化。Further, the etching method of the present invention is characterized in that the semiconductor film is etched using the etching liquid composition of the present invention, and the surface is roughened.
而且，本發明之蝕刻方法，其特徵為具備使用本發明之蝕刻液組成物進行的第1蝕刻步驟，為本發明之蝕刻液組成物，且使用與在前述第1蝕刻步驟中使用的蝕刻液組成物不同組成的蝕刻液組成物來進行之第2蝕刻步驟。Further, the etching method of the present invention is characterized in that it comprises a first etching step using the etching liquid composition of the present invention, and is an etching liquid composition of the present invention, and an etching liquid used in the first etching step is used. The second etching step is performed by using an etchant composition having a different composition.
另外，本發明之蝕刻方法，以蝕刻選自由AlGaInP膜、AlGaAs膜、GaAsP膜所成群之任一種的半導體膜時使用較佳。Further, the etching method of the present invention is preferably used when etching a semiconductor film selected from the group consisting of an AlGaInP film, an AlGaAs film, and a GaAsP film.
[發明效果][Effect of the invention]
藉由使用本發明之蝕刻液組成物，可在低溫且短時間內、有效地蝕刻半導體膜，在蝕刻面上形成凹凸形狀。另外，藉由選擇組成，可控制凹凸的形狀、凹凸的大小、蝕刻量等。而且，藉由適當選擇蝕刻步驟時之組成，可有效地進行蝕刻，使半導體膜之表面形成具有企求的凹凸之企求狀態。By using the etching liquid composition of the present invention, the semiconductor film can be efficiently etched at a low temperature for a short period of time, and an uneven shape can be formed on the etched surface. Further, by selecting the composition, the shape of the unevenness, the size of the unevenness, the amount of etching, and the like can be controlled. Further, by appropriately selecting the composition at the time of the etching step, etching can be performed efficiently, and the surface of the semiconductor film can be formed in an intended state with desired irregularities.
[為實施發明之形態][In order to implement the invention]
於下述中，詳細說明有關本發明之蝕刻液及蝕刻方法。In the following, the etching liquid and the etching method relating to the present invention will be described in detail.
本發明之蝕刻液組成物，含有無機酸與金屬化合物。其次，本發明之蝕刻液組成物中可使用的無機酸，例如鹽酸、磷酸、硫酸、硝酸等，較佳者為鹽酸與磷酸。The etching liquid composition of the present invention contains a mineral acid and a metal compound. Next, an inorganic acid which can be used in the composition of the etching liquid of the present invention, for example, hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid or the like, is preferably hydrochloric acid and phosphoric acid.
無機酸之濃度，只要是實用上可得企求的蝕刻形狀即可，以考慮AlGaInP膜之組成予以決定較佳。例如，為鹽酸時，濃度以1～30重量%之範圍較佳，以10～22重量%之範圍更佳。另外，為磷酸時，濃度以1～75重量%之範圍較佳，以40～70重量%之範圍更佳。The concentration of the inorganic acid may be determined as long as it is a practically desirable etching shape, and it 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, more preferably in the range of 10 to 22% by weight. Further, in the case of phosphoric acid, the concentration is preferably in the range of 1 to 75% by weight, more preferably in the range of 40 to 70% by weight.
而且，此等之無機酸，可單獨使用1種無機酸，或可組合2種以上之無機酸使用。Further, as the inorganic acid, one type of inorganic acid may be used alone or two or more types of inorganic acids may be used in combination.
本發明之蝕刻液組成物中可使用的金屬化合物，例如鐵系化合物。鐵系化合物例如氯化鐵、硫酸鐵、硝酸鐵、磷酸鐵、醋酸鐵、乳酸鐵、檸檬酸鐵等，其中，較佳者為氯化鐵與硫酸鐵。鐵系化合物濃度，只要是實用上可得企求的蝕刻形狀即可，就考慮AlGaInP膜之組成予以適當決定。為氯化鐵時，濃度以0.1～20重量%之範圍較佳，以1～15重量%之範圍更佳。另外，為硫酸鐵時，濃度以0.1～30重量%之範圍較佳，以1～20重量%之範圍更佳。A metal compound which can be used in the composition of the etching liquid of the present invention, for example, an iron-based compound. The iron-based compound is, for example, iron chloride, iron sulfate, iron nitrate, iron phosphate, iron acetate, iron lactate, iron citrate or the like, and among them, ferric chloride and iron sulfate are preferred. The concentration of the iron-based compound may be appropriately determined in consideration of the composition of the AlGaInP film as long as it is a practically available etching shape. In the case of ferric chloride, the concentration is preferably in the range of 0.1 to 20% by weight, more preferably in the range of 1 to 15% by weight. Further, in the case of ferric sulfate, the concentration is preferably in the range of 0.1 to 30% by weight, more preferably in the range of 1 to 20% by weight.
而且，此等之金屬化合物，可單獨使用，或可組合2種以上使用。Further, these metal compounds may be used singly or in combination of two or more.
此外，本發明之蝕刻液組成物中可使用的有機酸、及有機酸鹽，例如單羧酸、聚羧酸、氧化羧酸、膦酸、磺酸及其鹽。Further, an organic acid and an organic acid salt which can be used in the etching liquid composition of the present invention, for example, a monocarboxylic acid, a polycarboxylic acid, an oxidized carboxylic acid, a phosphonic acid, a sulfonic acid, and a salt thereof.
有機酸及有機酸鹽，具體而言例如甲酸、乙酸、丙酸等之單羧酸、草酸、丙二酸、琥珀酸、戊二酸等之聚羧酸、乙二醇酸、乳酸、蘋果酸、酒石酸、檸檬酸等之氧化羧酸、胺基三(亞甲基膦酸)、1-羥基亞乙基-1,1-二膦酸等之膦酸、甲烷磺酸、乙烷磺酸等之磺酸及其鹽等。Organic acids and organic acid salts, specifically, 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. , tartaric acid, citric acid, etc., oxidized carboxylic acid, amine tris (methylene phosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, etc., phosphonic acid, methanesulfonic acid, ethanesulfonic acid, etc. Sulfonic acid and its salts.
此外，有機酸鹽例如上述之有機酸的銨鹽、單乙醇胺、三乙醇胺等之有機胺鹽、四甲基氫氧化銨、四乙基氫氧化銨等之四級銨鹽、鈉、鉀等之鹼金屬鹽等。Further, the organic acid salt is, for example, an ammonium salt of the above organic acid, an organic amine salt such as monoethanolamine or triethanolamine, a quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide, sodium or potassium. Alkali metal salts and the like.
於有機酸及有機酸鹽之中，特別是較佳者如醋酸及醋酸鹽。而且，使用醋酸作為有機酸時，其濃度以1～70重量%之範圍較佳，以10～40重量%之範圍更佳。Among the organic acids and organic acid salts, particularly preferred are acetic acid and acetate. Further, when acetic acid is used as the organic acid, the concentration thereof is preferably in the range of 1 to 70% by weight, more preferably in the range of 10 to 40% by weight.
而且，此等之有機酸及有機酸鹽，可單獨使用，或可2種以上組合使用。Further, these organic acids and organic acid salts may be used singly or in combination of two or more kinds.
另外，本發明之蝕刻液組成物中可使用的界面活性劑，例如兩性界面活性劑、陰離子性界面活性劑、非離子性界面活性劑。Further, a surfactant which can be used in the etching liquid composition of the present invention, for example, an amphoteric surfactant, an anionic surfactant, or a nonionic surfactant.
兩性界面活性劑，具體而言例如全氟氧化胺系、全氟烷基甜菜鹼系、烷基氧化胺系、烷基甜菜鹼系等。The amphoteric surfactant is specifically, for example, a perfluoroamine oxide system, a perfluoroalkylbetaine system, an alkylamine oxide system, or an alkylbetaine system.
陰離子性界面活性劑，例如全氟烷基磺酸及其鹽、烷基磺酸及其鹽等。Anionic surfactants such as perfluoroalkylsulfonic acid and salts thereof, alkylsulfonic acids and salts thereof, and the like.
陰離子性界面活性劑，例如全氟烷基氧化胺、聚氧化乙烯烷醚等。Anionic surfactants, such as perfluoroalkyl amine oxides, polyoxyethylene alkyl ethers, and the like.
於界面活性劑中，特別是以使用兩性界面活性劑較佳。該兩性界面活性劑之濃度的較佳範圍，為0.001～1重量%之範圍，較佳者為0.005～0.1重量%之範圍。Among the surfactants, it is particularly preferred to use an amphoteric surfactant. The concentration of the amphoteric surfactant is preferably in the range of 0.001 to 1% by weight, preferably 0.005 to 0.1% by weight.
而且，本發明之蝕刻液組成物，通常作為水溶液使用，惟視其所需亦可與有機溶劑共存。Further, the etching liquid composition of the present invention is usually used as an aqueous solution, and may coexist with an organic solvent as needed.
此外，本發明之蝕刻液組成物，亦可另外與其他的添加劑共存。Further, the etching liquid composition of the present invention may additionally coexist with other additives.
本發明之蝕刻液組成物，可於對光阻之傷害小，以實施光罩的狀態進行蝕刻時使用，可製得精度高的蝕刻圖型。The composition of the etching liquid of the present invention can be used when etching is performed in a state where the mask is small in the case where the damage to the photoresist is small, and an etching pattern having high precision can be obtained.
另外，本發明之蝕刻液組成物，可在室溫下使用，且可得充分的蝕刻效果，惟視其所需亦可加熱使用。換言之，藉由適當選擇使用溫度等之條件，可得企求的蝕刻速度及蝕刻時間。Further, the etching liquid composition of the present invention can be used at room temperature, and a sufficient etching effect can be obtained, and it can be heated and used as needed. In other words, the desired etching rate and etching time can be obtained by appropriately selecting the conditions such as the use temperature.
此外，使用本發明之蝕刻液組成物的半導體膜之AlGaInP膜的蝕刻方法，例如將形成有AlGaInP膜之基板直接浸漬於蝕刻液中，且使基板本身靜止、搖動或攪拌蝕刻液、即藉由浸漬之方法，或藉由噴霧噴嘴將蝕刻液供應給基板之噴霧處理的方法等。Further, in the etching method of the AlGaInP film using the semiconductor film of the etching liquid composition of the present invention, for example, the substrate on which the AlGaInP film is formed is directly immersed in the etching liquid, and the substrate itself is allowed to stand still, shake or stir the etching liquid, that is, by A method of immersing, a method of spraying a etchant to a substrate by a spray nozzle, or the like.
而且，本發明之蝕刻液組成物，係藉由蝕刻半導體膜之表面，在半導體膜之表面上形成凹凸(粗面化)時使用，使用本發明之蝕刻液組成物，可有效地進行企求的蝕刻處理之半導體膜，例如AlGaInP膜、AlGaAs膜、GaAsP膜、GaInP膜、AlGaP膜、AlInP膜、GaP膜等。其中，特別是以蝕刻AlGaInP膜時使用為宜。Further, the etching liquid composition of the present invention is used by etching the surface of the semiconductor film to form irregularities (roughening) on the surface of the semiconductor film, and the etching liquid composition of the present invention can be effectively used. The semiconductor film to be etched, for example, an AlGaInP film, an AlGaAs film, a GaAsP film, a GaInP film, an AlGaP film, an AlInP film, a GaP film, or the like. Among them, it is preferable to use it especially when etching an AlGaInP film.
另外，使用本發明之蝕刻液組成物進行蝕刻時，可使用一定組成之蝕刻液組成物實施蝕刻，亦可使用不同組成之蝕刻液組成物實施蝕刻。Further, when etching is performed using the etching liquid composition of the present invention, etching may be performed using an etching liquid composition having a certain composition, or etching may be performed using an etching liquid composition having a different composition.
換言之，使用本發明之蝕刻液組成物進行蝕刻時，亦可使用一定的蝕刻液組成物實施第1蝕刻步驟，然後，使用與第1蝕刻步驟時使用的蝕刻液組成物不同組成的蝕刻液組成物，實施第2蝕刻步驟。In other words, when etching is performed using the etching liquid composition of the present invention, the first etching step may be performed using a predetermined etching liquid composition, and then an etching liquid having a composition different from that of the etching liquid composition used in the first etching step may be used. The second etching step is performed.
如此藉由使用不同組成之蝕刻液組成物實施蝕刻，可使半導體膜之表面具有企求的凹凸之企求狀態。By performing etching using the etching liquid compositions having different compositions, the surface of the semiconductor film can be made to have an undesired state of the irregularities.
於下述中，藉由實施例更具體地說明本發明，惟本發明不受此等實施例所限制。In the following, the invention will be more specifically illustrated by the examples, but the invention is not limited by the examples.
[蝕刻液組成物(試料)之製作][Production of Etchant Composition (Sample)]
使用鹽酸、磷酸、醋酸、乳酸、硫酸、過氧化氫(H2O2)、氯化鐵、硫酸鐵、硝酸鐵、全氟烷基氧化胺(兩性界面活性劑)、全氟烷基磺酸(陰離子性界面活性劑)等之原料。Use hydrochloric acid, phosphoric acid, acetic acid, lactic acid, sulfuric acid, hydrogen peroxide (H 2 O 2 ), ferric chloride, iron sulfate, iron nitrate, perfluoroalkyl amine oxide (amphoteric surfactant), perfluoroalkyl sulfonic acid Raw material such as (anionic surfactant).
藉由如表1所示之組成稱取此等之原料且溶解於水中，製作表1之試料編號1～15之各試料(蝕刻液組成物)。Each of the samples of the sample Nos. 1 to 15 of Table 1 (etching liquid composition) was prepared by weighing the raw materials of the compositions shown in Table 1 and dissolving them in water.
而且，試料編號1～10之試料為具備本發明要件之實施例的試料，試料編號11～15之試料為不具本發明要件之比較例的試料。Further, the samples of sample numbers 1 to 10 are samples having the examples of the requirements of the present invention, and the samples of sample numbers 11 to 15 are samples of the comparative examples not having the requirements of the present invention.
[評估試驗][evaluation test]
(1) 在表面上形成有半導體膜之評估用基板(1) A substrate for evaluation in which a semiconductor film is formed on a surface
評估如上述所製作的蝕刻液組成物之性能時，係使用在表面上形成有半導體膜之基板。When the performance of the etching liquid composition produced as described above was evaluated, a substrate on which a semiconductor film was formed on the surface was used.
該實施例係使用在GaAs基板上成膜有膜厚為2μm之AlGaInP膜的基板。In this embodiment, a substrate on which a film of AlGaInP having a film thickness of 2 μm was formed on a GaAs substrate was used.
(2) 評估方法(2) Evaluation method
以25℃、5分鐘之條件，將表面上形成有膜厚為2μm之AlGaInP膜之GaAs基板浸漬於如上述所製作的各蝕刻液中。A GaAs substrate having an AlGaInP film having a film thickness of 2 μm formed on the surface thereof was immersed in each of the etching liquids prepared as described above at 25 ° C for 5 minutes.
然後，自蝕刻液中取出GaAs基板，且進行水洗、乾燥後，以電子顯微鏡觀察，觀察AlGaInP膜之表面狀態，同時觀察凹凸之大小、蝕刻量、光阻是否受損的情形。其結果併記於表1。Then, the GaAs substrate was taken out from the etching solution, washed with water, dried, and observed under an electron microscope, and the surface state of the AlGaInP film was observed, and the size of the unevenness, the amount of etching, and whether the photoresist was damaged were observed. The results are also shown in Table 1.
而且，AlGaInP膜之表面狀態係表示在經蝕刻的表面上所形成的凹凸大小之狀態的概念，於表1中，◎A所表示者係表示在表面上較大的凹凸，藉由主要沿著結晶方位被蝕刻所得的表面狀態(參照第1圖)。此外，於表1中，◎B所表示者係表示在表面上較小的凹凸，藉由主要沒有沿著結晶方位被蝕刻所得的表面狀態(參照第2圖)。Further, the surface state of the AlGaInP film indicates the concept of the state of the unevenness formed on the etched surface. In Table 1, the person indicated by ◎A indicates a large unevenness on the surface by mainly along the surface. The surface state obtained by etching the crystal orientation is referred to (see Fig. 1). Further, in Table 1, the person indicated by ◎B indicates a small unevenness on the surface, and a surface state which is mainly obtained without etching along the crystal orientation (see Fig. 2).
此外，就抑制光反射且改善採光效率而言，通常以在表面上形成一定程度以上之大小的凹凸者較佳，惟形成小的凹凸時，亦具有採光的效率之改善效果，凹凸不一定必須為大者。Further, in order to suppress light reflection and improve lighting efficiency, it is generally preferable to form irregularities having a certain degree or more on the surface, but when small irregularities are formed, the effect of improving the efficiency of lighting is also obtained, and the unevenness is not necessarily required. For the big one.
另外，表1之凹凸大小，係使蝕刻後之AlGaInP膜形成凹凸的領域(經蝕刻的領域)中自凸部的頂部至凹部的底部之距離，使用顯微鏡所測定的值，表1係以具有寬度的值來表示複數處所測定的凹凸大小。In addition, the unevenness of Table 1 is a distance from the top of the convex portion to the bottom of the concave portion in the field in which the AlGaInP film after etching is formed (the field of etching), and the value measured using a microscope is shown in Table 1. The value of the width indicates the size of the concavity and convexity measured at the complex number.
而且，通常沿著結晶方位被蝕刻的程度為大時，會有形成大凹凸的傾向，沒有沿著結晶方位被蝕刻的程度大時，會有形成小凹凸的傾向。Further, when the degree of etching is generally large along the crystal orientation, large irregularities tend to be formed, and when the degree of etching is not large along the crystal orientation, small irregularities tend to be formed.
此外，上述之表面狀態與凹凸的大小，係對抑制AlGaInP膜之光全反射，提高採光效率的機能有很大的影響，惟為控制半導體膜之表面狀態或凹凸大小等時，係考慮半導體膜之種類等予以決定。Further, the above-mentioned surface state and the size of the concavities and convexities have a great influence on the function of suppressing total light reflection of the AlGaInP film and improving the light-receiving efficiency, and the semiconductor film is considered when controlling the surface state or the unevenness of the semiconductor film. The type and the like are determined.
另外，表1中之蝕刻量(深度)，係使用電子顯微鏡測定蝕刻處理前與蝕刻處理後之半導體膜的膜厚時，蝕刻處理前與蝕刻處理後之膜厚差。而且，於蝕刻處理後在蝕刻面上具有凹凸時，使用平均凹凸所求得的膜厚，求取蝕刻處理前後之膜厚的差作為蝕刻量。In addition, in the etching amount (depth) in Table 1, when the film thickness of the semiconductor film before the etching process and the etching process was measured using an electron microscope, the film thickness before the etching process and the etching process was inferior. Further, when the etching surface has irregularities on the etching surface, the film thickness obtained by the average unevenness is used, and the difference in film thickness before and after the etching treatment is determined as the etching amount.
而且，為確認是否有光阻受損的情形時，係在GaAs基板上塗佈例如正型光阻，予以曝光、顯影，形成光阻膜。Further, in order to confirm whether or not the photoresist is damaged, a positive resist is applied to the GaAs substrate, for example, and exposed and developed to form a photoresist film.
然後，以25℃、5分鐘之條件將形成有光阻膜之GaAs基板浸漬於試料編號1～15之各蝕刻液中後，觀察光阻膜，且觀察是否有受損情形。其結果併記於表1。Then, the GaAs substrate on which the photoresist film was formed was immersed in each of the etching liquids of Sample Nos. 1 to 15 at 25 ° C for 5 minutes, and then the photoresist film was observed and observed for damage. The results are also shown in Table 1.
(3) 評估結果(3) Evaluation results
如表1所示，使用試料編號11～15之不具本發明要件的比較例之試料(蝕刻液組成物)進行蝕刻時，在AlGaInP膜上沒有形成凹凸，而無法以可抑制光反射且提高採光效率的方式進行粗面化。As shown in Table 1, when the samples of the comparative examples (etching liquid compositions) of the sample Nos. 11 to 15 which do not have the requirements of the present invention were used for etching, no irregularities were formed on the AlGaInP film, and light reflection could not be suppressed and the daylighting could not be improved. The way of efficiency is roughened.
對此而言，使用試料編號1～10之具備本發明要件的蝕刻液組成物進行蝕刻處理時，可在AlGaInP膜上有效地形成表1所示形態的凹凸。On the other hand, when the etching liquid composition having the requirements of the present invention of Sample Nos. 1 to 10 is subjected to an etching treatment, irregularities in the form shown in Table 1 can be effectively formed on the AlGaInP film.
此外，由試料編號1～10之結果，可知具有具備本發明要件之組成的蝕刻液組成物時，藉由適當選擇組成，可控制表面狀態或凹凸大小、蝕刻量等，可以企求的狀態、有效地蝕刻半導體膜。In addition, as a result of the sample numbers 1 to 10, it is understood that when the composition of the etching liquid having the composition of the present invention is provided, the surface state, the size of the irregularities, the amount of etching, and the like can be controlled by appropriately selecting the composition, and the desired state can be effectively obtained. The semiconductor film is etched.
而且，有關光阻膜之受損情形，於使用試料編號15之比較例的蝕刻液時，確認光阻膜的受損情形。Further, in the case of the damage of the photoresist film, when the etching liquid of the comparative example of sample No. 15 was used, the damage of the photoresist film was confirmed.
另外，為試料編號1～10之本發明實施例的蝕刻液時，確認沒有光阻膜受損的情形。Further, in the case of the etching liquids of the examples of the present invention in Sample Nos. 1 to 10, it was confirmed that no photoresist film was damaged.
而且，該實施例係說明有關蝕刻作為半導體膜之AlGaInP膜時，惟本發明中半導體膜為AlGaAs膜、GaAsP膜、GaInP膜、AlGaP膜、AlInP膜、GaP膜時，確認亦可達成同樣的作用效果。Further, in this embodiment, when the AlGaInP film as the semiconductor film is etched, the semiconductor film in the present invention is an AlGaAs film, a GaAsP film, a GaInP film, an AlGaP film, an AlInP film, or a GaP film, and it is confirmed that the same effect can be achieved. effect.
此外，該實施例使用試料編號1～10之各蝕刻液進行蝕刻，惟使用本發明之蝕刻液組成物進行蝕刻時，亦可使用一定的蝕刻液組成物實施第1蝕刻步驟，然後，使用與第1蝕刻步驟使用的蝕刻液組成物不同組成的蝕刻液組成物實施第2蝕刻步驟。此時，可更為有效地控制表面狀態、或凹凸大小、蝕刻量等，製得具有企求凹凸之企求的表面狀態之半導體膜。Further, in this embodiment, etching is performed using each of the etching liquids of sample numbers 1 to 10. However, when etching is performed using the etching liquid composition of the present invention, the first etching step may be performed using a predetermined etching liquid composition, and then, The second etching step is performed on the etching liquid composition having different compositions of the etching liquid compositions used in the first etching step. At this time, the surface state, the size of the irregularities, the amount of etching, and the like can be more effectively controlled, and a semiconductor film having a surface state in which irregularities are desired can be obtained.
本發明之另一其他觀點中，不受上述實施例所限制，可於本發明之範圍內加入各種的應用、變化。In still another aspect of the present invention, various applications and changes can be added without departing from the scope of the invention.
[產業上之利用價值][Industry use value]
藉由使用本發明之蝕刻液組成物，使AlGaInP膜等之半導體膜進行蝕刻，可在低溫且短時間內在半導體膜之表面上形成企求的凹凸，可使直至目前之LED的製造步驟簡單化，且可提高生產量與減低成本。而且，本發明之蝕刻液組成物及使用它之蝕刻方法，可廣泛地利用於LED製造技術領域中。By etching the semiconductor film of an AlGaInP film or the like by using the etching liquid composition of the present invention, it is possible to form irregularities on the surface of the semiconductor film at a low temperature and in a short time, and the manufacturing steps of the LED up to the present can be simplified. And can increase production and reduce costs. Further, the etching liquid composition of the present invention and an etching method using the same can be widely utilized in the field of LED manufacturing technology.
[第1圖]係表示使用本發明實施例之蝕刻液，經蝕刻的半導體膜之表面狀態的典型圖，表1中◎A所表示的在表面上形成有較大的凹凸之狀態圖。[Fig. 1] is a view showing a state of the surface state of the etched semiconductor film using the etching liquid of the embodiment of the present invention, and a state in which a large unevenness is formed on the surface indicated by ◎A in Table 1.
[第2圖]係表示使用本發明實施例之蝕刻液，經蝕刻的半導體膜之表面狀態的典型圖，表1中◎B所表示的在表面上形成有較小的凹凸之狀態圖。[Fig. 2] is a view showing a state of the surface state of the etched semiconductor film using the etching liquid of the embodiment of the present invention, and a state in which a small unevenness is formed on the surface as indicated by ◎B in Table 1.
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| CN102732253A (en) * | 2012-06-30 | 2012-10-17 | 江阴润玛电子材料股份有限公司 | Ferric trichloride ITO etching solution and its preparation method |
| KR101898910B1 (en) * | 2012-07-10 | 2018-09-17 | 동우 화인켐 주식회사 | Etching paste compositon for offset-printing cliche |
| JP2014120695A (en) * | 2012-12-19 | 2014-06-30 | Rohm Co Ltd | Semiconductor light-emitting element |
| KR102092911B1 (en) * | 2014-03-28 | 2020-03-24 | 동우 화인켐 주식회사 | Soft etching agent of semiconductor light emitting layer, light emitting element and display element |
| CN105080216A (en) * | 2014-05-15 | 2015-11-25 | 浙江强盛滤料有限公司 | Preparation method of composite filter net of metal etching net and metal fiber net |
| KR102282955B1 (en) * | 2015-02-23 | 2021-07-28 | 동우 화인켐 주식회사 | Etching solution composition for indium oxide layer and manufacturing method of an array substrate for Liquid crystal display using the same |
| KR102259145B1 (en) * | 2015-03-26 | 2021-06-01 | 동우 화인켐 주식회사 | Etching solution composition for silver-containing layer and manufacturing method of an array substrate for display device using the same |
| TW201712890A (en) * | 2015-07-29 | 2017-04-01 | Nikkiso Co Ltd | Method for manufacturing light-emitting element |
| KR101922289B1 (en) * | 2015-11-26 | 2018-11-27 | 삼성에스디아이 주식회사 | Cmp slurry composition and polishing method of organic film using the same |
| KR102400258B1 (en) * | 2017-03-28 | 2022-05-19 | 동우 화인켐 주식회사 | Etchant composition for etching metal layer and manufacturing method of forming conductive pattern using the same |
| CN107151104A (en) * | 2017-06-12 | 2017-09-12 | 合肥市惠科精密模具有限公司 | A kind of TFT LCD glass substrate etching solution additives |
| KR102554816B1 (en) * | 2018-04-23 | 2023-07-12 | 삼성디스플레이 주식회사 | Echant composition and manufacturing method of metal pattern using the same |
| CN110644003B (en) * | 2018-06-26 | 2022-06-21 | 东友精细化工有限公司 | Silver thin film etching solution composition, etching method using same, and method for forming metal pattern |
| KR102661845B1 (en) * | 2018-10-11 | 2024-04-30 | 삼성디스플레이 주식회사 | Echtant and method for manufacturing display device using the same |
| TW202035361A (en) * | 2018-12-12 | 2020-10-01 | 美商3M新設資產公司 | Fluorinated amine oxide surfactants |
| KR102654172B1 (en) * | 2019-03-13 | 2024-04-03 | 주식회사 이엔에프테크놀로지 | Etchant composition for silver-containing metal layer |
| CN112397624B (en) * | 2019-08-16 | 2021-12-07 | 山东浪潮华光光电子股份有限公司 | Manufacturing method of GaP rough surface of GaAs-based LED wafer |
| CN110862825A (en) * | 2019-11-25 | 2020-03-06 | 苏州博洋化学股份有限公司 | Etching liquid for etching indium tin oxide semiconductor transparent conductive film |
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| US20080149885A1 (en) * | 2006-12-22 | 2008-06-26 | Shenzhen Futaihong Precision Industry Co.,Ltd. | Etchant for etching workpieces made of aluminum and aluminum alloys |
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