WO2015041214A1 - Liquide de gravure pour substrat de semi-conducteur - Google Patents

Liquide de gravure pour substrat de semi-conducteur Download PDF

Info

Publication number
WO2015041214A1
WO2015041214A1 PCT/JP2014/074442 JP2014074442W WO2015041214A1 WO 2015041214 A1 WO2015041214 A1 WO 2015041214A1 JP 2014074442 W JP2014074442 W JP 2014074442W WO 2015041214 A1 WO2015041214 A1 WO 2015041214A1
Authority
WO
WIPO (PCT)
Prior art keywords
etching
semiconductor substrate
sulfonic acid
etching solution
present
Prior art date
Application number
PCT/JP2014/074442
Other languages
English (en)
Japanese (ja)
Inventor
山本　裕三
斎田　利典
伸 大八木
義輝 鎌田
Original Assignee
攝津製油株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 攝津製油株式会社 filed Critical 攝津製油株式会社
Priority to JP2015537925A priority Critical patent/JP6373271B2/ja
Priority to CN201480050156.9A priority patent/CN105518834B/zh
Publication of WO2015041214A1 publication Critical patent/WO2015041214A1/fr

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0236—Special surface textures
    • H01L31/02363—Special surface textures of the semiconductor body itself, e.g. textured active layers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
    • C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to an etching solution for a semiconductor substrate, particularly an etching solution for a semiconductor substrate for a solar cell. Furthermore, this invention relates to the etching power recovery agent, the manufacturing method of the semiconductor substrate for solar cells, and the semiconductor substrate for solar cells.
  • Patent Document 1 discloses that an alkaline etching solution contains a specific aliphatic carboxylic acid and silicon to stabilize the etching rate when etching the substrate surface, and to achieve a desired size. A method of uniformly forming the pyramid-shaped irregularities on the substrate surface is described.
  • the present invention has been made in order to solve the above-mentioned problems, and its purpose is not to cause the above-mentioned environmental problems and quality fluctuations.
  • An object of the present invention is to provide an etching solution with excellent pyramid size control. It is another object of the present invention to provide a technique for uniformly forming irregularities of a desired size on a substrate surface even when a large number of solar cell semiconductor substrates are continuously etched.
  • the inventors of the present invention have made extensive studies to solve the above problems. As a result, it has been found that the use of lignin sulfonic acid and / or a salt thereof satisfying certain conditions can greatly improve the surface quality and texture structure homogeneity, is excellent in productivity, and can be greatly improved in continuous use.
  • the present invention has been completed.
  • the gist of the present invention is as follows.
  • An alkaline etching solution for treating the surface of a semiconductor substrate for solar cells which contains at least one selected from the group consisting of lignin sulfonic acid and salts thereof.
  • An etching power recovering agent which is added to the etching liquid after treating the semiconductor substrate for solar cells with the etching liquid according to the above [1], and recovers the etching power of the etching liquid.
  • n is an integer of 0 to 5, and each R is independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms
  • Etching power recovery agent for an etchant comprising at least one selected from the group consisting of lignin sulfonic acid and a salt of lignin sulfonic acid
  • a method for producing a solar cell semiconductor substrate comprising an etching step of etching the substrate surface of the solar cell semiconductor substrate with the etching solution according to [1] to form irregularities on the substrate surface;
  • a semiconductor substrate for a solar cell the surface of which is etched with the etching solution according to [1].
  • the present invention it is possible to form a texture in a shorter time on a relatively low temperature side, and the effect of excellent productivity is exhibited.
  • the surface defects are reduced, a texture having excellent surface quality can be formed.
  • the etching solution of the present invention is an alkaline aqueous solution for treating the surface of a semiconductor substrate for solar cells, contains at least one alkaline component, and contains lignin sulfonic acid and / or a salt thereof that satisfy certain conditions. It is characterized by that. Further, at least one selected from a specific sulfonic acid compound and a salt thereof, and silicic acid and / or silicate may be included.
  • the etching solution of the present invention is alkaline. Specifically, the pH at 25 ° C. is preferably in the range of 12 to 14, and preferably in the range of 13 to 14.
  • the pH of the etching solution can be set within a desired range by appropriately changing the amount and concentration of an alkali agent described later.
  • Lignin sulfonic acid and its salts Lignin sulfonic acid or lignin sulfonate, which is a compound obtained by treating pulp waste liquor by-produced during pulp production by various methods, and the main component is lignin sulfonate or lignin sulfonic acid.
  • the chemical structure of lignin is a compound with a phenylpropane group as the basic skeleton, and a three-dimensional network structure.
  • Lignin sulfonic acid and lignin sulfonate are given various names depending on the isolation method. For example, when lignin is obtained as a residue, lignin sulfate, lignin hydrochloride, copper ammonium lignin, periodate lignin and the like can be mentioned.
  • Inorganic reagent lignin sulfonic acid, alkali lignin, thiolignin, chlorlignin, 2) Acidic organic reagent: alcohol lignin, dioxane lignin, phenol lignin, thioglycolic acid Lignin, acetate lignin, hydrotropic lignin, 3) by hydrochloric acid organic reagent: Brauns natural lignin, acetone lignin, Nord lignin, Bjorkman lignin and the like. Lignin sulfonic acid or a salt thereof obtained by sulfonation using the above isolated lignin or a derivative thereof may be used.
  • lignin sulfonic acid and lignin sulfonate that have been chemically modified, such as increasing the carboxyl group by oxidation treatment, can also be used.
  • the lignin sulfonic acid and lignin sulfonate that can be used in the present invention may contain impurities during pulp production, but the smaller the amount, the better. When there are many impurities, shape collapse will occur in a part of the pyramid or the uniformity of the pyramid shape is impaired.
  • Lignin sulfonic acid and lignin sulfonate are manufactured and sold by a large number of pulp manufacturers.
  • the molecular weight ranges from 1.8 to 1,000,000 and is rich in variety such as various sulfonation degrees, various salts, chemically modified products, and those prepared with heavy metal ions.
  • the present inventors have found that not all of these various lignin sulfonic acids and salts thereof are suitable for the purpose of the present invention, and that the effect varies depending on the thing, or a specific lignin sulfonic acid or a salt thereof.
  • the present inventors have found that anisotropic etching of a silicon semiconductor substrate proceeds well, a concavo-convex structure (pyramid shape) is formed well, and the achievement of the object of the present invention is greatly improved.
  • the lignin sulfonic acid or a salt thereof that can be suitably used in the present invention satisfies all the following conditions 1) to 3).
  • a low molecular component having a molecular weight of less than 1000 and a high molecular component having a molecular weight of 100,000 or more are very little or completely removed. Specifically, the molecular weight distribution has a peak between 1000 and 100,000, preferably between 2000 and 60,000, and at least 50% by mass or more of the component is present in this molecular weight region.
  • Sulfone group density ie, degree of sulfonation
  • Those having 0 to 3 carboxyl groups per 500 molecular weight units Those having 0 to 3 carboxyl groups per 500 molecular weight units.
  • the measurement of molecular weight and molecular weight distribution in said 1) is implemented by the GPC (gel permeation chromatography) method shown below.
  • A Sample preparation Add the same weight of water to the sample to prepare a sample for GPC.
  • B Column A guard column TSX (manufactured by Tosoh Corporation), one HXL (6.5 mm ⁇ ⁇ 4 cm), one TSK3000HXL (7.8 mm ⁇ ⁇ 30 cm), and one TSK2500HXL (7.8 mm ⁇ ⁇ 30 cm) are used. Connect guard column-3000HXL-2500HXL in order from the inlet side.
  • C Standard material Polystyrene (manufactured by Tosoh Corporation) is used.
  • the type of lignin sulfonate that can be used in the present invention is not particularly limited, and the above lignin sulfonic acid Na salt, K salt, Ca salt, ammonium salt, Cr salt, Fe salt, Al salt, Mn salt, Mg Any salt or the like can be used in the present invention.
  • lignin sulfonic acid or a salt thereof obtained by chelating heavy metal ions such as Fe, Cr, Mn, Mg, Zn, and Al can be used in the present invention.
  • lignin sulfonic acid or a salt thereof further added with another organic compound or organic polymer such as naphthalene or phenol can also be used in the present invention.
  • the concentration of “at least one selected from the group consisting of lignin sulfonic acid and its salt” in the etching solution of the present invention is preferably in the range of, for example, 0.001 ppm or more and 10,000 ppm or less. From the viewpoint of effectively removing bubbles generated during the etching process, and further efficiently forming irregularities on the substrate surface, particularly pyramid shape, the concentration is preferably 0.001 ppm or more, more preferably 0.1 ppm or more, 2 ppm or more is more preferable, and 20 ppm or more is more preferable. On the other hand, it is preferably 10,000 ppm or less, more preferably 1000 ppm or less, and even more preferably 500 ppm or less from the viewpoint of making the unevenness formed, particularly the pyramid shape, and the etching rate.
  • the lignin sulfonic acid or lignin sulfonate contained in the etching solution of the present invention is obtained by sulfonating a pulp waste solution as a raw material. Moreover, by including it in an alkaline etching solution together with the following sulfonic acid compound represented by the following general formula (I) and / or silicic acid and / or silicate, initial rise and texture quality can be further improved. .
  • the sulfonic acid compound represented by the following general formula (I) has less unpleasant odor compared to aliphatic carboxylic acids such as caprylic acid and heptanoic acid. Work environment can be improved.
  • n is an integer of 0 to 5, and each R is independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.
  • N is preferably 1 or more and 5 or less.
  • n is 1 or more, it is preferable because the etching process of the substrate surface can be promoted, and when n is 5 or more, it is not preferable because the etching process is hindered.
  • a more preferable range of n is 1 or more and 3 or less.
  • the alkyl group having 1 to 12 carbon atoms may be linear or branched.
  • an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group is particularly preferable.
  • the number of carbon atoms is within the above preferred range, the number of carbon atoms of the hydrocarbon group of the compound represented by the general formula (I) is reduced. As a result, the BOD (biochemical oxygen demand) and COD (chemical oxygen demand) of the etching solution can be reduced.
  • the substitution position of R on the benzene ring is preferably the para-position or ortho-position of the sulfo group, and particularly preferably the para-position of the sulfo group.
  • sulfonic acid compounds represented by the general formula (I) benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid and cumenesulfonic acid are more preferable, and such a sulfonic acid compound may be used alone. Or two or more types may be used in combination.
  • toluenesulfonic acid pyramidal irregularities having a desired size can be formed uniformly on the substrate surface.
  • toluenesulfonic acid is less odorous than aliphatic carboxylic acids such as caprylic acid. Therefore, if toluenesulfonic acid is used, the working environment such as etching can be improved.
  • the preferred toluenesulfonic acid is para-toluenesulfonic acid (PTS).
  • the concentration of the sulfonic acid compound in the etching solution of the present invention is not particularly limited, but is preferably 0.005 to 2.0 mol / L. If the said density
  • silicic acid and / or silicate The kind of silicic acid and / or silicate contained in the etching solution of the present invention is not particularly limited, but is preferably at least one selected from the group consisting of metal silicon, silica, silicic acid and silicate.
  • the silicate is preferably an alkali metal silicate, for example, sodium silicate such as sodium orthosilicate (Na 4 SiO 4 .nH 2 O) and sodium metasilicate (Na 2 SiO 3 .nH 2 O), Examples thereof include potassium silicates such as K 4 SiO 4 .nH 2 O and K 2 SiO 3 .nH 2 O, and lithium silicates such as Li 4 SiO 4 .nH 2 O and Li 2 SiO 3 .nH 2 O. These silicates can be used by adding the compound itself to the etching solution, or by directly dissolving silicon materials such as silicon wafers, silicon ingots, silicon cutting powders, etc. or silicon dioxide in an alkali as a reaction product. The obtained silicate compound may be used as a silicate. In the present invention, JIS No. 1 silicate is preferable from the viewpoint of availability.
  • the content of silicic acid and / or silicate in the etching solution of the present invention (the content of silicic acid when containing only silicic acid, the content of silicate when containing only silicate, silicic acid and When silicate is included, the total amount thereof is not particularly limited, but is preferably 0.01 to 10 wt%, more preferably 0.1 to 5 wt%, and still more preferably 0.2 to 3 wt%. It is.
  • the silicon material or silicon dioxide is dissolved and supplied, the above concentration range is preferable in terms of Si atoms.
  • the content of the above silicic acid and / or silicate affects the stabilization of the etching rate.
  • the content of silicic acid and / or silicate that stabilizes the etching rate varies depending on conditions such as the alkali concentration described later and the temperature of the etching solution during etching. For this reason, what is necessary is just to determine the content of the optimal silicic acid and / or silicate according to the density
  • Alkali is a component necessary for forming pyramidal irregularities on the substrate surface when the substrate surface is etched with an etching solution.
  • the type of alkali contained in the etching solution of the present invention is not particularly limited, and both organic alkali and inorganic alkyl can be used.
  • organic alkali for example, a quaternary ammonium salt such as tetramethylammonium hydroxide, an alkanolamine and the like are preferable.
  • inorganic alkali hydroxides of alkali metals and alkaline earth metals such as sodium hydroxide, potassium hydroxide and calcium hydroxide are preferable, and sodium hydroxide or potassium hydroxide is particularly preferable. These alkalis may be used alone or in combination of two or more.
  • the concentration of alkali in the etching solution is not particularly limited, but is preferably 0.1% by mass or more and 50% by mass or less. From the viewpoint of exerting an etching effect, 0.1% by mass or more is preferable, 0.5% by mass or more is more preferable, 1% by mass or more is more preferable, 2% by mass or more is more preferable, and 3% by mass or more is more preferable. . On the other hand, from the viewpoint of cost effectiveness, 50% by mass or less is preferable, 30% by mass or less is more preferable, and 25% by mass or less is more preferable. In particular, when the alkali concentration is 3% by mass or more, the durability of the etching solution is remarkably increased, and even when the etching solution is repeatedly used, irregularities of a desired size can be uniformly formed on the substrate surface.
  • the etching solution of the present invention may contain other components as long as the effects of the present invention are not impaired.
  • a chelating agent, an amino acid, a polymer, glycol ethers, etc. as an auxiliary agent, the effect (incident incident light is efficiently taken into the substrate) by including the sulfonic acid compound can be enhanced.
  • the solvent of the etching solution of the present invention is preferably water.
  • the method for adjusting the etching solution of the present invention is not particularly limited, and a conventionally known method can be employed.
  • the composition of the etching solution of the present invention is preferably in the above-mentioned composition range when used, but the composition at the time of shipment can also be made into a conch in order to reduce transportation costs. 2-5 times conch shipping is preferable.
  • the etching solution of the present invention has a high effect of recovering the etching power of the deteriorated etching solution when a new etching solution is added to the etching solution gradually deteriorated by etching the semiconductor substrate for solar cells.
  • the above high etching power recovery effect can be obtained by replacing or adding 10% or more of the etching solution with a new etching solution. Therefore, the etching solution of the present invention can be used as an etching power recovery agent.
  • the sulfonic acid compound containing the alkaline agent and represented by the general formula (I) a salt of the sulfonic acid compound, the lignin sulfonic acid, and the lignin sulfonic acid It contains at least one selected from the group consisting of these salts.
  • Etching power can be recovered by adding an alkaline agent to an etching solution that has deteriorated due to repeated processing of a semiconductor substrate for solar cells. Furthermore, in order to improve the uniformity of the pyramid shape and the uniformity of the entire surface, the sulfonic acid compound represented by the general formula (I), the salt of the sulfonic acid compound, the lignin sulfonic acid and the lignin By adding the above sulfonic acid compound alone or in combination with an alkali agent from a sulfonic acid salt, the number of etching treatment batches can be increased without replacing the deteriorated etching solution. As a result, the initial building bath etching solution can be used continuously, so that the industrial value is enhanced.
  • the sulfonic acid compound represented by the general formula (I) the salt of the sulfonic acid compound, the lignin sulfonic acid and the lignin
  • the manufacturing method of the semiconductor substrate for solar cells of this invention is equipped with the etching process of etching the board
  • a single crystal silicon substrate is preferable, but a single crystal semiconductor substrate using a semiconductor compound such as copper / indium or gallium arsenide can also be used.
  • the method of bringing the etching solution of the present invention into contact with the substrate surface is not particularly limited, but a method of immersing the semiconductor substrate for solar cells in the etching solution is preferable.
  • the production method of the present invention will be described with reference to the method of immersion.
  • the etching step in the dipping method is, for example, a step of putting the etching solution of the present invention in a predetermined container and immersing the solar cell semiconductor substrate therein.
  • the temperature of the etching solution in the container is not particularly limited and can be set as appropriate, but it is preferably in the range of 70 to 98 ° C. in consideration of production and quality.
  • the immersion time of the solar cell semiconductor substrate in the etching solution in the etching step is not particularly limited and can be appropriately set. However, considering production and quality, it is preferably 10 to 40 minutes.
  • the etching solution of the present invention since the etching solution of the present invention is used, pyramidal irregularities of a desired size are uniformly formed on the substrate surface of a larger number of semiconductor substrates for solar ionization than before. Can be formed. Furthermore, what has a composition of the etching agent of this invention can be added in an etching tank as an etching power recovery agent which recovers etching power. By using an etching power recovery agent in this way, the number of continuous use of the etching process can be increased, which is preferable.
  • the semiconductor substrate for solar cells manufactured by the manufacturing method of the present invention is a semiconductor substrate for solar cells manufactured using the etching solution of the present invention, and the substrate surface has a maximum side length of 1 to 30 ⁇ m at the bottom,
  • the upper limit is preferably 25 ⁇ m, more preferably the upper limit is 20 ⁇ m, and pyramid-shaped uniform irregularities are formed.
  • a semiconductor substrate for solar cells with high productivity and low reflectance can be obtained.
  • the pyramidal irregularities are convex portions formed by arranging pyramidal (quadrangular pyramidal) convex portions on the surface of the semiconductor substrate for solar cells.
  • the size of the pyramid shape formed on the substrate surface is preferably 1 to 30 ⁇ m, more preferably 2 to 20 ⁇ m, and even more preferably 2 to 15 ⁇ m. From the viewpoint of reducing light reflectance, the average size is preferably 1 ⁇ m or more, and from the viewpoint of productivity, the average size is preferably 30 ⁇ m or less.
  • pyramidal irregularities of a desired size are formed without gaps on the surface of the semiconductor substrate for a solar cell formed by etching using the etching solution of the present invention. Therefore, the semiconductor substrate surface for solar cells formed by etching using a conventionally known etching solution and the semiconductor substrate surface for solar cells formed by etching using the etching solution of the present invention have pyramidal unevenness. A distinction can be made based on the size variation, the size of the interval between the pyramidal projections, and the like.
  • Examples 1-22 and Comparative Examples 1-2 A single crystal silicon substrate (one side 156 mm square, thickness 150 ⁇ m) having a crystal orientation (100) plane was immersed in an etching aqueous solution prepared according to the formulation shown in Table 1 at 80 to 90 ° C. for 10 to 30 minutes. .
  • Table 1 shows the results obtained by observing the substrate surface after the etching treatment with the naked eye, a laser microscope, and a scanning electron microscope. A specific etching process is as described in [Etching process] below.
  • Examples 23 to 27 and Comparative Examples 3 to 4 Concerning the stamina of the etching solution (continuous use), a large number of substrates (31 sheets / cassette) are set in a substrate support cassette for an etching solution amount of 30 L, and this is processed multiple times as a batch, and the quality of the pyramid Evaluation was made based on the number of batches in which a reference value was set and maintained. At that time, the consumption of alkali was intense, so the consumed KOH was determined by an automatic titrator, and 0.5 to 1.5 times equivalent KOH was replenished every batch.
  • a specific etching process is as described in [Etching process] below.
  • Example 27 of continuous usability p-toluenesulfonic acid (PTS) and lignin sulfonic acid were added in the 18th batch, and the continuous test was continued.
  • the additional amount of PTS was an amount that increased the concentration of PTS in the etching solution by 3% by weight
  • the additional amount of lignin sulfonic acid was an amount that increased the concentration of lignin sulfonic acid in the etching solution by 100 ppm.
  • the conditions and results are shown in Table 2. The number of times of continuous use was evaluated by the number of times when the substrate was evaluated to be ⁇ .
  • Bubble streaks Vertical traces due to bubble traces and liquid flow may be seen starting from the part where the wafer and jig claw contact on the jig (cassette) holding the wafer in the etching tank. The degree was determined by visual observation as follows. A: Strong vertical stripes are not seen. B: Although some vertical stripes are observed, it is an allowable range (a range that is not noticeable when a solar cell panel is used). C: Longitudinal streaks are somewhat strong. F: Strong vertical stripes are observed.
  • Tekali A phenomenon in which unevenness of the pyramid structure is not formed, the (100) mirror surface remains as it is, and it becomes a surface property that reflects light and looks like a mirror. The degree is classified and judged as follows.
  • C Some shine is present.
  • F Tekari is recognized on the entire surface.
  • Pyramid size The surface of the substrate is observed with a laser microscope, and the pyramid size is measured for 10 pyramid shapes from the largest. This was performed for 3 fields of view and averaged to obtain an average pyramid size. The results are shown in Table 1. Some of the substrates were also observed with a scanning electron microscope.
  • the above laser microscope uses Keyence Corporation's Laser Microscope VK-X100, photographed at 100x objective lens (20x eyepiece), 2000x magnification, printed on paper, and the bottom size of the pyramid Measurement was made and the base size was defined as a pyramid size.
  • the scanning electron microscope was JSM-5310 manufactured by JEOL Ltd., and the acceleration voltage was observed at 15 kV.
  • Pyramid size uniformity The determination was made based on the existence ratio of a small pyramid size of 50% or less of the average pyramid size of the laser microscope. A: Less than 50% of the average pyramid size is less than 20%. B: 20-40% of the above is present. C: 40% or more of the above is present.
  • Examples 1 to 22 using a specific lignin sulfonic acid showed excellent etching characteristics despite a relatively low temperature (85 ° C.) and a short time (15 minutes), and uniform surface quality (no uneven appearance) It can be seen that the uniformity of the pyramid size is also excellent. Moreover, there is no occurrence of a shining surface (location where pyramids are not formed), which is good. The light reflectance is also kept low. It can be seen that Comparative Examples 1 and 2 are significantly inferior to the Examples in terms of surface quality (appearance unevenness and bubble streaks).
  • Example 27 As shown in Examples 23 to 27, it can be seen that good continuous use characteristics are exhibited. In Example 27, it turns out that the frequency
  • the etching solution of the present invention can be used as an etching solution when etching the surface of a semiconductor substrate for solar cells.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Computer Hardware Design (AREA)
  • Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Photovoltaic Devices (AREA)
  • Weting (AREA)

Abstract

La présente invention porte sur un liquide de gravure alcalin pour traiter la surface d'un substrat de semi-conducteur pour une batterie solaire, le liquide de gravure comprenant au moins un élément sélectionné parmi le groupe comprenant un acide sulfonique de lignine et des sels de celui-ci. Une utilisation du liquide de gravure selon la présente invention présente les effets d'une excellente productivité et d'être apte à former une texture en une courte quantité de temps à des températures relativement faibles. En outre, le liquide de gravure produit les effets de l'affinement et de l'excellente élimination en surface des bulles qui sont générées en grandes quantités durant un traitement multi-feuille, et le rendement est augmenté en raison du fait que la flottement d'un substrat durant une gravure peut être éliminé. De plus, des textures ayant une excellente qualité de surface peuvent être formées en raison du fait que les défauts de surface sont réduits.
PCT/JP2014/074442 2013-09-19 2014-09-16 Liquide de gravure pour substrat de semi-conducteur WO2015041214A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2015537925A JP6373271B2 (ja) 2013-09-19 2014-09-16 半導体基板用エッチング液
CN201480050156.9A CN105518834B (zh) 2013-09-19 2014-09-16 半导体基板用蚀刻液

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013-194574 2013-09-19
JP2013194574 2013-09-19

Publications (1)

Publication Number Publication Date
WO2015041214A1 true WO2015041214A1 (fr) 2015-03-26

Family

ID=52688864

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/074442 WO2015041214A1 (fr) 2013-09-19 2014-09-16 Liquide de gravure pour substrat de semi-conducteur

Country Status (4)

Country Link
JP (1) JP6373271B2 (fr)
CN (1) CN105518834B (fr)
TW (1) TWI600799B (fr)
WO (1) WO2015041214A1 (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016063881A1 (fr) * 2014-10-21 2016-04-28 攝津製油株式会社 Liquide de gravure pour substrat semiconducteur
WO2017188177A1 (fr) * 2016-04-27 2017-11-02 攝津製油株式会社 Liquide de gravure destiné à un substrat semi-conducteur
WO2021158301A1 (fr) * 2020-02-05 2021-08-12 Advansix Resins & Chemicals Llc Tensioactifs pour l'électronique
US11525105B2 (en) 2019-12-20 2022-12-13 Advansix Resins & Chemicals Llc Surfactants for cleaning products
US11542428B2 (en) 2019-12-31 2023-01-03 Advansix Resins & Chemicals Llc Surfactants for oil and gas production
US11571377B2 (en) 2019-12-19 2023-02-07 Advansix Resins & Chemicals Llc Surfactants for use in personal care and cosmetic products
EP4148808A1 (fr) * 2021-09-14 2023-03-15 Zhejiang Jinko Solar Co., Ltd. Cellule solaire, procédé de fabrication de cellule solaire et module photovoltaïque
US11633481B2 (en) 2019-12-20 2023-04-25 Advansix Resins & Chemicals Llc Surfactants for use in healthcare products
US11905304B2 (en) 2019-12-19 2024-02-20 Advansix Resins & Chemicals Llc Surfactants for agricultural products
US11952394B2 (en) 2019-08-22 2024-04-09 Advansix Resins & Chemicals Llc Siloxane derivatives of amino acids having surface-active properties

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005019605A (ja) * 2003-06-25 2005-01-20 Naoetsu Electronics Co Ltd テクスチャー形成用エッチング液
JP2007258656A (ja) * 2006-02-23 2007-10-04 Sanyo Electric Co Ltd 凹凸基板の製造方法及び光起電力素子の製造方法
JP2012004528A (ja) * 2010-05-18 2012-01-05 Shinryo Corp エッチング液およびシリコン基板の表面加工方法
WO2012023613A1 (fr) * 2010-08-20 2012-02-23 株式会社トクヤマ Composition de formation de texture, procédé de production d'un substrat en substrat et kit de préparation de composition de formation de texture
JP2012114449A (ja) * 2010-11-24 2012-06-14 Air Products & Chemicals Inc シリコンウェハーのテクスチャ形成用の組成物及び方法
JP2013089629A (ja) * 2011-10-13 2013-05-13 Shinryo Corp エッチング液およびシリコン基板の表面加工方法
US20130130508A1 (en) * 2011-09-02 2013-05-23 Air Products And Chemicals, Inc. Compositions and Methods for Texturing of Silicon Wafers
WO2014010471A1 (fr) * 2012-07-09 2014-01-16 攝津製油株式会社 Fluide de gravure, agent de récupération de force de gravure, procédé de fabrication d'un substrat semi-conducteur destiné à une cellule solaire, et substrat semi-conducteur destiné à une cellule solaire

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007214412A (ja) * 2006-02-10 2007-08-23 Toshiba Corp 半導体基板洗浄方法
JP4795430B2 (ja) * 2006-05-02 2011-10-19 三益半導体工業株式会社 半導体基板の製造方法及びエッチング液
JP2008291312A (ja) * 2007-05-24 2008-12-04 Sumitomo Precision Prod Co Ltd 基板処理装置
WO2011114675A1 (fr) * 2010-03-16 2011-09-22 三菱電機株式会社 Procédé de gravure d'une plaquette de silicium, solution d'attaque, dispositif de gravure, et dispositif semi-conducteur
CN103290484A (zh) * 2012-02-28 2013-09-11 靖江市精益化学品有限公司 用于单晶硅制绒过程中不补加且无醇的第四代添加剂

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005019605A (ja) * 2003-06-25 2005-01-20 Naoetsu Electronics Co Ltd テクスチャー形成用エッチング液
JP2007258656A (ja) * 2006-02-23 2007-10-04 Sanyo Electric Co Ltd 凹凸基板の製造方法及び光起電力素子の製造方法
JP2012004528A (ja) * 2010-05-18 2012-01-05 Shinryo Corp エッチング液およびシリコン基板の表面加工方法
WO2012023613A1 (fr) * 2010-08-20 2012-02-23 株式会社トクヤマ Composition de formation de texture, procédé de production d'un substrat en substrat et kit de préparation de composition de formation de texture
JP2012114449A (ja) * 2010-11-24 2012-06-14 Air Products & Chemicals Inc シリコンウェハーのテクスチャ形成用の組成物及び方法
US20130130508A1 (en) * 2011-09-02 2013-05-23 Air Products And Chemicals, Inc. Compositions and Methods for Texturing of Silicon Wafers
JP2013089629A (ja) * 2011-10-13 2013-05-13 Shinryo Corp エッチング液およびシリコン基板の表面加工方法
WO2014010471A1 (fr) * 2012-07-09 2014-01-16 攝津製油株式会社 Fluide de gravure, agent de récupération de force de gravure, procédé de fabrication d'un substrat semi-conducteur destiné à une cellule solaire, et substrat semi-conducteur destiné à une cellule solaire

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10106736B2 (en) 2014-10-21 2018-10-23 Settsu Oil Mill., Inc. Etching agent for semiconductor substrate
WO2016063881A1 (fr) * 2014-10-21 2016-04-28 攝津製油株式会社 Liquide de gravure pour substrat semiconducteur
WO2017188177A1 (fr) * 2016-04-27 2017-11-02 攝津製油株式会社 Liquide de gravure destiné à un substrat semi-conducteur
US11952394B2 (en) 2019-08-22 2024-04-09 Advansix Resins & Chemicals Llc Siloxane derivatives of amino acids having surface-active properties
US11905304B2 (en) 2019-12-19 2024-02-20 Advansix Resins & Chemicals Llc Surfactants for agricultural products
US11571377B2 (en) 2019-12-19 2023-02-07 Advansix Resins & Chemicals Llc Surfactants for use in personal care and cosmetic products
US11633481B2 (en) 2019-12-20 2023-04-25 Advansix Resins & Chemicals Llc Surfactants for use in healthcare products
US11525105B2 (en) 2019-12-20 2022-12-13 Advansix Resins & Chemicals Llc Surfactants for cleaning products
US11542428B2 (en) 2019-12-31 2023-01-03 Advansix Resins & Chemicals Llc Surfactants for oil and gas production
US11891568B2 (en) 2019-12-31 2024-02-06 Advansix Resins & Chemicals Llc Surfactants for oil and gas production
US11427760B2 (en) 2020-02-05 2022-08-30 Advansix Resins & Chemicals Llc Surfactants for electronics
WO2021158301A1 (fr) * 2020-02-05 2021-08-12 Advansix Resins & Chemicals Llc Tensioactifs pour l'électronique
EP4148808A1 (fr) * 2021-09-14 2023-03-15 Zhejiang Jinko Solar Co., Ltd. Cellule solaire, procédé de fabrication de cellule solaire et module photovoltaïque

Also Published As

Publication number Publication date
TWI600799B (zh) 2017-10-01
JP6373271B2 (ja) 2018-08-15
CN105518834B (zh) 2018-02-16
TW201520376A (zh) 2015-06-01
JPWO2015041214A1 (ja) 2017-03-02
CN105518834A (zh) 2016-04-20

Similar Documents

Publication Publication Date Title
JP6373271B2 (ja) 半導体基板用エッチング液
KR101922855B1 (ko) 규소 기판의 표면을 처리하기 위한 수성 알칼리 조성물 및 방법
KR101407988B1 (ko) 에칭액 및 실리콘 기판의 표면가공 방법
TW201209157A (en) Aqueous alkaline etching and cleaning composition and method for treating the surface of silicon substrates
JP2012114449A (ja) シリコンウェハーのテクスチャ形成用の組成物及び方法
WO2012144461A1 (fr) Composition liquide de gravure et procédé de gravure
JP2010141139A (ja) シリコン基板のエッチング液およびシリコン基板の表面加工方法
WO2014010471A1 (fr) Fluide de gravure, agent de récupération de force de gravure, procédé de fabrication d'un substrat semi-conducteur destiné à une cellule solaire, et substrat semi-conducteur destiné à une cellule solaire
WO2016063881A1 (fr) Liquide de gravure pour substrat semiconducteur
KR101608610B1 (ko) 텍스처 형성용 에칭액
JP2013089629A (ja) エッチング液およびシリコン基板の表面加工方法
WO2017188177A1 (fr) Liquide de gravure destiné à un substrat semi-conducteur
JP2016092228A (ja) エッチング液、半導体基板の製造方法、半導体基板および太陽電池
KR20200047184A (ko) 상온에서 적용가능한 상온탈지제 및 이를 이용한 탈지방법
JP6157895B2 (ja) テクスチャー形成用組成物、シリコン基板の製造方法、及びテクスチャー形成用組成物調製キット
EP2557147B1 (fr) Compositions aqueuses alcalines et procédé de traitement de la surface de substrats de silicium
JP2003313584A (ja) 洗浄剤組成物
KR20120127308A (ko) 기판의 텍스처링 조성물 및 이를 이용하는 방법
JP2012038830A (ja) テクスチャー形成用組成物

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14846571

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2015537925

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14846571

Country of ref document: EP

Kind code of ref document: A1