WO2012043365A1 - Etching fluid composition and etching method - Google Patents

Etching fluid composition and etching method Download PDF

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WO2012043365A1
WO2012043365A1 PCT/JP2011/071583 JP2011071583W WO2012043365A1 WO 2012043365 A1 WO2012043365 A1 WO 2012043365A1 JP 2011071583 W JP2011071583 W JP 2011071583W WO 2012043365 A1 WO2012043365 A1 WO 2012043365A1
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etching
acid
etching solution
solution composition
film
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PCT/JP2011/071583
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French (fr)
Japanese (ja)
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謙司 勇
木村　真弓
次広 田湖
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林純薬工業株式会社
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Priority to KR1020127033030A priority Critical patent/KR20130113336A/en
Priority to CN201180046558.8A priority patent/CN103125017B/en
Publication of WO2012043365A1 publication Critical patent/WO2012043365A1/en

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    • 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

Definitions

  • 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.
  • the LEDs generally require 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.
  • AlGaInP films have been used in yellow-green to red high-brightness LEDs.
  • a method for roughening the surface of this AlGaInP 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 thereto (see Patent Document 4), Etc. have been proposed.
  • a technique using dry etching has been proposed as a technique for making the surface of the AlGaInP film uneven.
  • 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.
  • 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.
  • 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
  • an AlGaInP film can be roughened (roughened) at a low temperature and in a short time, and further studies and experiments were conducted to complete the present invention.
  • the etching solution composition of the present invention is An etching solution used to roughen the surface of a semiconductor film by etching the surface, (a) an inorganic acid; (b) including a metal compound.
  • the etching solution of the present invention is further characterized in that it contains at least one selected from the group consisting of (c) an organic acid, an organic acid salt, an inorganic acid salt, and a surfactant.
  • the inorganic acid is preferably at least one selected from the group consisting of hydrochloric acid, phosphoric acid, sulfuric acid and nitric acid.
  • the metal compound contains an iron-based compound.
  • 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.
  • 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.
  • the organic acid is preferably acetic acid.
  • 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.
  • the surfactant is preferably at least one selected from the group consisting of amphoteric surfactants, anionic surfactants, and nonionic surfactants.
  • the inorganic acid is hydrochloric acid
  • the metal compound is iron chloride
  • the organic acid is acetic acid
  • the etching solution composition of the present invention is characterized in that it is used for etching any semiconductor film selected from the group consisting of an AlGaInP film, an AlGaAs film, and a GaAsP film.
  • the etching method of the present invention is characterized in that the semiconductor film is etched using the etching solution composition according to the present invention to roughen the surface.
  • the etching method of the present invention includes a first etching step performed using the etching solution composition according to the present invention, and an etching solution composition according to the present invention, the etching method used in the first etching step. And a second etching performed using an etching solution composition having a composition different from that of the liquid composition.
  • the etching method of the present invention is preferably applied to etch any semiconductor film selected from the group consisting of an AlGaInP film, an AlGaAs film, and a GaAsP film.
  • the etching solution composition of the present invention By using the etching solution composition of the present invention, it is possible to efficiently etch the semiconductor film 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, it is possible to efficiently perform etching so that the surface of the semiconductor film has a desired state having unevenness as intended.
  • FIG. 1 It is a figure which shows typically the surface state of the semiconductor film etched using the etching liquid concerning the Example of this invention, Comprising: The state by which comparatively large unevenness
  • FIG. It is a figure which shows typically the surface state of the semiconductor film etched using the etching liquid concerning the Example of this invention, Comprising: The state in which comparatively small unevenness
  • the etching solution composition of the present invention contains an inorganic acid and a metal compound.
  • 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.
  • 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.
  • 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.
  • the concentration is preferably in the range of 1 to 75% by weight, more preferably in the range of 40 to 70% by weight.
  • 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.
  • Examples of the metal compound that can be used in the etching solution composition of the present invention include iron-based compounds.
  • 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.
  • iron chloride it is preferably in the range of 0.1 to 20% by weight, more preferably in the range of 1 to 15% by weight.
  • iron sulfate it is preferably in the range of 0.1 to 30% by weight, more preferably in the range of 1 to 20% by weight.
  • these metal compounds may be used independently and may be used in combination of 2 or more type.
  • 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.
  • 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.
  • 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
  • alkali metal salts such as potassium
  • organic acids and organic acid salts acetic acid and acetate are particularly preferable.
  • the concentration is preferably in the range of 1 to 70% by weight, and more preferably in the range of 10 to 40% by weight.
  • organic acids and organic acid salts may be used alone or in combination of two or more.
  • examples of the surfactant that can be used in the etching solution composition of the present invention include amphoteric surfactants, anionic surfactants, and nonionic surfactants.
  • amphoteric surfactants include perfluoroamine oxides, perfluoroalkyl betaines, alkylamine oxides, and alkyl betaines.
  • anionic surfactant examples include perfluoroalkyl sulfonic acid and its salt, alkyl sulfonic acid and its salt, and the like.
  • nonionic surfactants include perfluoroalkylamine oxide and polyoxyethylene alkyl ether.
  • amphoteric surfactants are particularly preferably used.
  • a preferable range of the concentration of the amphoteric surfactant is in the range of 0.001 to 1% by weight, and more preferably in the range of 0.005 to 0.1% by weight.
  • etching liquid composition of this invention is normally used as aqueous solution, depending on the case, an organic solvent can also coexist.
  • etching solution composition of the present invention can further coexist with other additives.
  • the etching solution composition of the present invention causes little damage to the resist, can be used for etching with a resist mask applied, and can obtain an etching pattern with high accuracy.
  • the etching solution composition of the present invention can be used at room temperature to obtain a sufficient etching effect, but can also be used by heating depending on the application. That is, a desired etching rate and etching time can be obtained by appropriately selecting conditions such as operating temperature.
  • 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.
  • 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.
  • 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.
  • 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.
  • the surface state of the AlGaInP film is a concept indicating the state of the size of the unevenness formed on the etched surface, and in Table 1, those indicated as ⁇ 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).
  • 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.
  • 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.
  • 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.
  • a positive resist was applied, exposed and developed on a GaAs substrate to form a resist film.
  • 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.
  • 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.
  • etching was performed using each of the etching liquids of sample numbers 1 to 10.
  • a predetermined etching liquid composition was used. It is also possible to carry out the first etching step and then carry out the second etching step using an etching solution composition having a composition different from that 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.
  • the etching solution composition of the present invention By etching a semiconductor film such as an 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 in a short time.
  • the manufacturing process can be simplified to improve the throughput and reduce the cost. 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.

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Abstract

A composition is adopted that includes an inorganic acid and a metal compound. The composition further includes an organic acid, an organic acid salt, an inorganic acid salt, or a surfactant. The composition further includes hydrochloric acid, phosphoric acid, sulfuric acid, or nitric acid, as the inorganic acid. Furthermore, an iron-based compound is used as the metal compound. At least one acid selected from a group comprising monocarboxylic acid, polycarboxylic acid, oxycarboxylic acid, phosphonic acid, sulfonic acid and salts thereof is used as the organic acid and the organic acid salt. Using the etching fluid composition according to the present invention, a semiconductor film of AlGaInP film, AlGaAs film or GaAsP film is etched, and the surface is made rough.

Description

エッチング液組成物およびエッチング方法Etching solution composition and etching method
　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。 LEDs generally require 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 yellow-green to red high-brightness LEDs. 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 thereto (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 actually not 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.
特開平５－３２６４８５号JP-A-5-326485 特開平２－２６０６３６号JP-A-2-260636 特開２００１－２６７３０７号JP 2001-267307 A 特開２００７－１９４５３６号JP 2007-194536 A 特開２００６－１０８６３５号JP 2006-108635 A 特開２００７－５９５１８号JP 2007-59518 A
　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、
　半導体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であって、
　(ａ)無機酸と、
　(ｂ)金属化合物と
　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 was found that an AlGaInP film can be roughened (roughened) at a low temperature and in a short time, and further studies and experiments were conducted to complete the present invention.
That is, the etching solution composition of the present invention is
An etching solution used to roughen the surface of a semiconductor film by etching the surface,
(a) an inorganic acid;
(b) including a metal compound.
　本発明のエッチング液は、さらに、(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。 The etching solution of the present invention is further characterized in that it contains at least one selected from the group consisting of (c) an organic acid, an organic acid salt, an inorganic acid salt, and a surfactant.
　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 the metal compound contains an iron-based 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液組成物は、ＡｌＧａＩｎＰ膜、ＡｌＧａＡｓ膜、ＧａＡｓＰ膜からなる群より選ばれるいずれかの半導体膜をエッチングするのに用いられるものであることを特徴としている。 The etching solution composition of the present invention is characterized in that it is used for etching any semiconductor film selected from the group consisting of an AlGaInP film, an AlGaAs film, and a GaAsP film.
　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半導体膜をエッチングし、表面を粗面化することを特徴としている。 Further, the etching method of the present invention is characterized in that the semiconductor 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、本発明にかかるエッチング液組成物を用いて行う第１のエッチング工程と、本発明にかかる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行う第２のエッチングと
　を備えていることを特徴としている。 Moreover, the etching method of the present invention includes a first etching step performed using the etching solution composition according to the present invention, and an etching solution composition according to the present invention, the etching method used in the first etching step. And a second etching performed using an etching solution composition having a composition different from that of the liquid composition.
　また、本発明のエッチング方法は、ＡｌＧａＩｎＰ膜、ＡｌＧａＡｓ膜、ＧａＡｓＰ膜からなる群より選ばれるいずれかの半導体膜をエッチングするのに適用することが好ましい。 The etching method of the present invention is preferably applied to etch any semiconductor film selected from the group consisting of an AlGaInP film, an AlGaAs film, and a GaAsP film.
　本発明のエッチング液組成物を用いることにより、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、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, it is possible to efficiently etch the semiconductor film 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, it is possible to efficiently perform etching so that the surface of the semiconductor film has a desired state having unevenness as intended.
本発明の実施例にかかるエッチング液を用いてエッチングした半導体膜の表面状態を模式的に示す図であって、表１に◎Ａとして示した、表面に比較的大きな凹凸が形成された状態を示す図である。It is a figure which shows typically the surface state of the semiconductor film etched using the etching liquid concerning the Example of this invention, Comprising: The state by which comparatively large unevenness | corrugation was formed in the surface shown as (double-circle) A in Table 1 is shown. FIG. 本発明の実施例にかかるエッチング液を用いてエッチングした半導体膜の表面状態を模式的に示す図であって、表１に◎Ｂとして示した、表面に比較的小さい凹凸が形成された状態を示す図である。It is a figure which shows typically the surface state of the semiconductor film etched using the etching liquid concerning the Example of this invention, Comprising: The state in which comparatively small unevenness | corrugation was formed on the surface shown as (double-circle) B in Table 1 FIG.
　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, 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, it is preferably in the range of 0.1 to 20% by weight, more preferably in the range of 1 to 15% by weight. In the case of iron sulfate, it is preferably in the range of 0.1 to 30% by weight, more preferably in the range of 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。 Also, 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. When acetic acid is used as the organic acid, the concentration is preferably in the range of 1 to 70% by weight, and more preferably in the range of 10 to 40% by 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。 Also, examples of the surfactant 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, perfluoroalkyl betaines, alkylamine oxides, and alkyl betaines.
　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 in the range of 0.001 to 1% by weight, and more preferably in the range of 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 causes little damage to the resist, can be used for etching with a resist mask applied, and can obtain an etching pattern with high accuracy.
　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。 The etching solution composition of the present invention can be used at room temperature to obtain a sufficient etching effect, but can also be used by heating depending on the application. 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。 Hereinafter, the present invention will be described more specifically by way of examples. However, 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１～１０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 (H2O2), iron chloride, iron sulfate, iron nitrate, perfluoroalkylamine oxide (amphoteric surfactant), perfluoroalkylsulfonic acid (anionic surfactant) ) Etc. 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.
Note that samples Nos. 1 to 10 are samples of Examples having the requirements of the present invention, and Samples Nos. 11 to 15 are samples of Comparative Examples not having the requirements of the present invention.
［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.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　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。 Note that the surface state of the AlGaInP film is a concept indicating the state of the size of the unevenness formed on the etched surface, and in Table 1, those indicated as ◎ 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 the light extraction efficiency by suppressing the reflection of light, 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。 Note that, generally, when the degree of etching along the crystal orientation is large, large irregularities are formed, and when the degree of etching is large regardless of the crystal orientation, small irregularities tend to be formed.
　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。 Further, 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。 Then, the GaAs substrate on which the resist film was formed was immersed in each of the etching solutions of sample numbers 1 to 15 at 25 ° C. for 5 minutes, and then the resist film was observed to check for damage. 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 did not satisfy 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１～１０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 having the requirements of the present invention of sample numbers 1 to 10, the AlGaInP film is efficiently formed with unevenness in the manner shown in Table 1. I was able to.
　また、試料番号１～１０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。 Further, from the results of sample numbers 1 to 10, in the case of an etching solution composition having a composition satisfying the requirements of the present invention, 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１～１０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 films were not damaged in the case of the etching solutions according to the examples of the present invention with sample numbers 1 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、試料番号１～１０の各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。 Further, in this example, etching was performed using each of the etching liquids of sample numbers 1 to 10. However, when performing etching using the etching liquid composition of the present invention, a predetermined etching liquid composition was used. It is also possible to carry out the first etching step and then carry out the second etching step using an etching solution composition having a composition different from that 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 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膜などの半導体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 a semiconductor film such as an 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 in a short time. The manufacturing process can be simplified to improve the throughput and reduce the cost. 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 (14)

  1. 半導体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であって、
    　(ａ)無機酸と、
    　(ｂ)金属化合物と
    　を含むことを特徴とするエッチング液組成物。     An etching solution used to roughen the surface of a semiconductor film by etching the surface,
    (a) an inorganic acid;
    (b) An etching solution composition comprising: a metal compound.
  2. さらに、(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請求項１記載のエッチング液組成物。 The etching solution composition according to claim 1, further comprising (c) at least one selected from the group consisting of an organic acid, an organic acid salt, an inorganic acid salt, and a surfactant.
  3. 前記無機酸が、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種であることを特徴とする請求項１記載のエッチング液組成物。 2. The etching solution composition according to claim 1, wherein the inorganic acid is at least one selected from the group consisting of hydrochloric acid, phosphoric acid, sulfuric acid, and nitric acid.
  4. 前記金属化合物として、鉄系化合物を含むことを特徴とする請求項１記載のエッチング液組成物。 The etching solution composition according to claim 1, wherein the metal compound includes an iron-based compound.
  5. 前記鉄系化合物が、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種であることを特徴とする請求項４記載のエッチング液組成物。 5. The etching according to claim 4, wherein the iron-based compound is at least one selected from the group consisting of iron chloride, iron nitrate, iron sulfate, iron phosphate, iron acetate, iron lactate, and iron citrate. Liquid composition.
  6. 前記有機酸および前記有機酸塩が、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種であることを特徴とする請求項２記載のエッチング液組成物。 3. The organic acid and the organic acid salt are at least one selected from the group consisting of monocarboxylic acids, polycarboxylic acids, oxycarboxylic acids, phosphonic acids, sulfonic acids and salts thereof. Etching solution composition.
  7. 前記有機酸が、酢酸であることを特徴とする請求項２記載のエッチング液組成物。 The etching solution composition according to claim 2, wherein the organic acid is acetic acid.
  8. 前記無機酸塩が、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種であることを特徴とする請求項２記載のエッチング液組成物。 The etching solution composition according to claim 2, wherein the inorganic acid salt is at least one selected from the group consisting of salts of hydrochloric acid, phosphoric acid, sulfuric acid, and nitric acid.
  9. 前記界面活性剤が、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種であることを特徴とする請求項２記載のエッチング液組成物。 The etching solution composition according to claim 2, wherein the surfactant is at least one selected from the group consisting of amphoteric surfactants, anionic surfactants, and nonionic surfactants.
  10. 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を特徴とする請求項２記載のエッチング液組成物。 The etching solution composition according to claim 2, wherein the inorganic acid is hydrochloric acid, the metal compound is iron chloride, and the organic acid is acetic acid.
  11. ＡｌＧａＩｎＰ膜、ＡｌＧａＡｓ膜、ＧａＡｓＰ膜からなる群より選ばれるいずれかの半導体膜をエッチングするのに用いられるものであることを特徴とする請求項１記載のエッチング液組成物。 2. The etching solution composition according to claim 1, wherein the etching solution composition is used for etching any semiconductor film selected from the group consisting of an AlGaInP film, an AlGaAs film, and a GaAsP film.
  12. 請求項１記載のエッチング液組成物を用いて半導体膜をエッチングし、表面を粗面化することを特徴とするエッチング方法。 An etching method comprising etching a semiconductor film using the etching solution composition according to claim 1 to roughen the surface.
  13. 請求項１記載のエッチング液組成物を用いて行う第１のエッチング工程と、
    　請求項１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。     A first etching step performed using the etching solution composition according to claim 1;
    The etching solution composition according to claim 1, comprising a second etching step performed using an etching solution composition having a composition different from that of the etching solution composition used in the first etching step. An etching method characterized by the above.
  14. ＡｌＧａＩｎＰ膜、ＡｌＧａＡｓ膜、ＧａＡｓＰ膜からなる群より選ばれるいずれかの半導体膜をエッチングするものであることを特徴とする請求項１２記載のエッチング方法。 13. The etching method according to claim 12, wherein the semiconductor film selected from the group consisting of an AlGaInP film, an AlGaAs film, and a GaAsP film is etched.
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