CN105936823A - Composite for etching treatment and etching treatment method - Google Patents
Composite for etching treatment and etching treatment method Download PDFInfo
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- CN105936823A CN105936823A CN201610124361.6A CN201610124361A CN105936823A CN 105936823 A CN105936823 A CN 105936823A CN 201610124361 A CN201610124361 A CN 201610124361A CN 105936823 A CN105936823 A CN 105936823A
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- 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
- C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
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- 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
Abstract
The invention aims to provide a composite for etching treatment capable of forming inverted pyramid shaped texture on surfaces of to-be-treated objects such as a silicone substrate at a low cost and with small environmental influence and through safety and convenient operation. The composite used for etching treatment provided by the invention contains nitrogenous aromatic heterocyclic compound and hydrogen fluoride.
Description
Technical field
The present invention relates to etch processes compositions and use the etching of this etch processes compositions
Processing method.
Background technology
Solaode is most important technology as global warming countermeasure in recent years, concentrates
Strength is developed.In the exploitation of solaode, efficiency enhancement scheme is extremely important, but
It is that efficiency based on material improves and there is limit, the most just carries in research equipment efficiency on the whole
High scheme.
As improved efficiency scheme, it is known that if able to the light improved on equipment sensitive surface absorbs effect
Rate, then can go far towards to improve efficiency.Therefore, by silicon substrate such as monocrystal silicon
The optimization of texture structure and the antiradar reflectivity of light and the sunken light effect that obtain get most of the attention, just
In the forming method actively studying this texture structure.
It is about the texture structure of this silicon substrate, different because of shape to the effect of conversion efficiency,
Its excellence degree is following sequence: honeycomb shape ＞ inverted pyramid shape ＞ Pyramid ＞ volcano
Mouth-shaped.
For the texture structure of honeycomb shape, formed on a silicon substrate with plasma CVD and cover
Film, carries out perforation processing by laser patterning.Afterwards, by use fluorine nitric acid etc. each to
Same sex Wet-type etching, forms hemispherical hole, its process number at silicon substrate with the closeest configuration
Many, cost is high, is not practical (with reference to non-patent literature 1 etc.).
For the texture structure of inverted pyramid shape, generally, crystalline silicon substrate is used mask,
Being formed by operation based on photoetching, therefore process number is many, and cost is high, not by general (reference
Non-patent literature 2 etc.).
Pyramid is the texture formed by carrying out alkali etching on the monosilicon, the most
General and low cost, but the reason that constructs because of pyramid of the sunken light effect of sunlight and the highest.
The texture when texture of crater shape is to be etched polysilicon with acid, loses with alkalescence
Carve same low cost, but the sunken light effect of sunlight is minimum among these textures.
As above in the technology of silicon substrate formation texture structure, the present invention sends out
A person of good sense develops the method different from existing etching processing method, i.e. as etch processes
The thin film containing the organic compound with N-F key is formed, by right on the solid material of object
This thin film is exposed and is etched processing.
In the etching processing method of the present inventor's exploitation, by there is having of N-F key
Machine compound coats the surface of the solid materials such as silicon substrate, makes this cloth cover expose, it is thus possible to
Enough textures (with reference to patent documentation 1 etc.) forming inverted pyramid shape at solid material surface.
As it has been described above, the etching processing method of the present inventor's exploitation is can be by simplicity
Operation, form the antiradar reflectivity of light and/or high the falling of sunken light effect at solid material surface
The epoch-making method of Pyramid, but, use in an etching process has N-F key
The purchase cost of organic compound high, therefore towards needing to solve the problem on cost with changing.
Prior art literature
Patent documentation
Patent documentation 1: International Publication the 2009/119848th
Non-patent literature
Non-patent literature 1:J.Plasma Fusion Res., Vol.85, No.12 (2009), p.829-832
Non-patent literature 2:M.A.Green et al, Very high efficiency silicon solar
cells science and technology,IEEE TRANSACTION ON ELECTRON
DEVICES,46(1999),p.1940-1947
Summary of the invention
Invention to solve the technical problem that
The invention that the present invention is contemplated to solve above-mentioned problem and makes, its object is to provide one
Kind of low cost, little on the impact of environment, can be by safety and easy operation at silicon substrate etc.
The surface of treated object forms etch processes compositions and the use of the texture of inverted pyramid shape
The etching processing method of this etch processes compositions.
Technical teaching for solving the problem was
The present inventor has been repeated further investigation, and result is it was surprisingly found that lead to
Cross use and comprise the nitrogenous aromatic heterocyclic compounds such as pyridine and the compositions of fluohydric acid gas, it is possible to solve
Certainly above-mentioned problem.And then, by using the etch processes of said composition, it is possible at treated object
The texture of upper formation inverted pyramid shape.The present inventor is based on relevant knowledge, by being repeated
Further research, thus complete the present invention.
That is, the present invention provides etch processes compositions described in following item typically
With the etching processing method using this etch processes compositions.
1. 1 kinds of etch processes compositionss of item, it contains nitrogenous aromatic heterocyclic compounds and fluorine
Change hydrogen.
The item 2. etch processes compositionss as described in above-mentioned item 1, wherein, nitrogenous aromatic series
Heterocyclic compound is pyridine or derivatives thereof.
3. etch processes compositionss as described in above-mentioned item 2, wherein, pyridine or its spread out
Biology is the compound shown in following formula (1).
[in formula, adjacent R1And R2、R2And R3、R3And R4Or R4And R5Can connect
And form-CR6=CR7-CR8=CR9-, R1、R2、R3、R4、R5、R6、R7、R8、
And R9Represent: hydrogen atom identical or differently；Halogen atom；Nitro；Hydroxyl；Cyano group；Ammonia
Base formoxyl；Can have selected from halogen atom, hydroxyl, the alkoxyl of carbon number 1～5,
The aryloxy group of carbon number 6～10, the acyl group of carbon number 2～5, carbon number 2～5
The carbon number 1～15 of at least one substituent group in the aryl of acyloxy and carbon number 6～10
Alkyl；Can have at least 1 in the aryl of halogen atom and carbon number 6～10
Plant the thiazolinyl of the carbon number 1～15 of substituent group；Can have selected from halogen atom and carbon atom
The alkynyl of the carbon number 1～15 of at least one substituent group in the aryl of several 6～10；Permissible
The carbon with at least one substituent group in the alkyl of halogen atom and carbon number 1～5 is former
The aryl of subnumber 6～15；Can have at least one halogen atom substituent carbon number 1～
The acyl group of 15；Can have in the aryl of halogen atom and carbon number 6～10 at least
The alkoxy carbonyl group of the carbon number 2～15 of a kind of substituent group；Can have selected from halogen atom and carbon
The aryloxy carbonyl of the carbon number 7～15 of at least one substituent group in the alkyl of atomic number 1～5；
Can have at least one substituent group in the aryl of halogen atom and carbon number 6～10
The alkyl sulphonyl of carbon number 1～15；Can have selected from halogen atom and carbon number
The aryl sulfonyl of the carbon number 6～15 of at least one substituent group in the alkyl of 1～5；Can
To have at least one substituent group in the aryl of halogen atom and carbon number 6～10
The alkyl sulphinyl of carbon number 1～15；Can have selected from halogen atom and carbon number
The aryl sulfonyl kia of the carbon number 6～15 of at least one substituent group in the alkyl of 1～5；
Can have at least one substituent group in the aryl of halogen atom and carbon number 6～10
The alkoxyl of carbon number 1～15；Can have selected from halogen atom and carbon number 1～5
Alkyl in the aryloxy group of carbon number 6～15 of at least one substituent group；Can have to
The acyloxy of the carbon number 1～15 of few a kind of halogen atom substituent；Can have at least 1
Plant the acyl sulfenyl of the carbon number 1～15 of halogen atom substituent；Can have selected from halogen former
The carbon number 1～15 of at least one substituent group in the aryl of son and carbon number 6～10
Alkane sulfonyl oxy；Can have in the alkyl of halogen atom and carbon number 1～5 extremely
The aryl-sulfonyl oxygen of the carbon number 6～15 of few a kind of substituent group；Can have selected from carbon former
The amino of at least one substituent group in the alkyl of subnumber 1～5 and the aryl of carbon number 6～10
Formoxyl；Can have at least one in the acyl group and halogen atom of carbon number 1～5
The amino of substituent group；Can have selected from halogen atom, the aryl of carbon number 6～10 and carbon
The N-alkylated pyrazole of the carbon number 6～15 of at least one substituent group in the alkyl of atomic number 1～5
Pyridine alkali；Can have selected from halogen atom, the aryl of carbon number 6～10 and carbon number
The N-aryl pyridinium salt of the carbon number 11～15 of at least one substituent group in the alkyl of 1～5
Base；Or organic polymer chain.]
The item 4. etch processes compositionss described in as any one of above-mentioned item 1～3, wherein,
This etch processes compositions is possibly together with oxidant.
The item 5. etch processes compositionss as described in above-mentioned item 4, wherein, oxidant is selected from
At least one in the oxide of hydrogen peroxide, peracetic acid and nitrogenous aromatic heterocyclic compounds.
6. 1 kinds of etching processing methods, this etching processing method include (1) make above-mentioned item 1～
The operation that etch processes compositions described any one of 5 contacts with treated object.
Item 7. etching processing methods as described in above-mentioned item 6, wherein, this etching processing method
Also include the operation of (2-1) heating treated object.
Item 8. etching processing methods as described in above-mentioned item 6 or 7, wherein, this etch processes
Method also includes: (2-2) can shine in the face contacted with etch processes compositions of treated object
Penetrate the operation of energy line.
Item 9. etching processing methods described in as any one of above-mentioned item 6～8, wherein, quilt
Processed material is semi-conducting material or insulating material.
10. 1 kinds of etch processes things of item, this etch processes thing is by arbitrary in above-mentioned item 6～9
Etching processing method described in Xiang obtains.
11. 1 kinds of solaodes of item, this solaode comprises the erosion described in above-mentioned item 10
Carve processed material.
The effect of invention
In accordance with the invention it is possible to the impact with low cost, on environment is little, by safe and easy
Operation the surface of treated object formed inverted pyramid shape texture.
Accompanying drawing explanation
Fig. 1 is the skeleton diagram of the etch processes of embodiment 1～3.
Fig. 2 is surface and the cross section of the silicon substrate obtained by the etch processes of embodiment 1
SEM image.Wherein, in Fig. 2, it is labeled as the surface of the graphical representation silicon substrate on " surface "
SEM image, be labeled as the SEM image in the cross section of the graphical representation silicon substrate in " cross section ".
Fig. 3 is surface and the cross section of the silicon substrate obtained by the etch processes of embodiment 2
SEM image.Wherein, in Fig. 3, it is labeled as the surface of the graphical representation silicon substrate on " surface "
SEM image, be labeled as the SEM image in the cross section of the graphical representation silicon substrate in " cross section ".
Fig. 4 is surface and the cross section of the silicon substrate obtained by the etch processes of embodiment 3
SEM image.Wherein, in Fig. 4, it is labeled as the surface of the graphical representation silicon substrate on " surface "
SEM image, be labeled as the SEM image in the cross section of the graphical representation silicon substrate in " cross section ".
Fig. 5 be by embodiment 1～3 and the etch processes of reference example 2 obtain silicon substrate, with
And it is etched the SEM image on the surface of silicon substrate before treatment (reference example 1).Wherein,
In Fig. 5, after etch processes compositions is coated silicon substrate by " processing the time (dividing) " expression,
The time placed in darkroom.
Fig. 6 is the skeleton diagram of the etch processes of embodiment 4～16.
Fig. 7 is the SEM image on the surface of the silicon substrate obtained by the etch processes of embodiment 4.
Fig. 8 is the SEM image on the surface of the silicon substrate obtained by the etch processes of embodiment 5.
Fig. 9 is the SEM image on the surface of the silicon substrate obtained by the etch processes of embodiment 6.
Wherein, in fig .9, the amplification graphical representation of part that will surround with broken circle in upper image
In bottom.
Figure 10 is that the SEM on the surface of the silicon substrate obtained by the etch processes of embodiment 7 is schemed
Picture.
Figure 11 is that the SEM on the surface of the silicon substrate obtained by the etch processes of embodiment 8 is schemed
Picture.
Figure 12 is that the SEM on the surface of the silicon substrate obtained by the etch processes of embodiment 9 is schemed
Picture.Wherein, in fig. 12, the enlarged drawing picture of part that will surround with broken circle in upper image
Represent in bottom.
Figure 13 is that the SEM on the surface of the silicon substrate obtained by the etch processes of embodiment 10 is schemed
Picture.
Figure 14 is that the SEM on the surface of the silicon substrate obtained by the etch processes of embodiment 11 is schemed
Picture.Wherein, in fig. 14, the enlarged drawing picture of part that will surround with broken circle in upper image
Represent in bottom.
Figure 15 be obtained by the etch processes of embodiment 7～9 and 12～16 silicon substrate, with
And the SEM image on the surface of the silicon substrate (reference example 3) before etch processes.
Figure 16 is the skeleton diagram of the etch processes of embodiment 17～22.
Figure 17 is the surface of the silicon substrate obtained by the etch processes of embodiment 17～22
SEM image.
Figure 18 is that the SEM on the surface of the silicon substrate obtained by the etch processes of embodiment 23 is schemed
Picture.Wherein, in figure 18, by the amplification graphical representation of left-side images on right side.
Figure 19 is that the SEM on the surface of the silicon substrate obtained by the etch processes of embodiment 24 is schemed
Picture.Wherein, Tu19Zhong, observes in the operation 1 of the graphical representation embodiment 24 of upper left quarter
The graphical representation of the SEM image of silicon substrate, upper right quarter and right lower quadrant is in embodiment 24
The SEM image of the silicon substrate observed in operation 5.Further, by upper right quarter image with void
The amplification graphical representation of the part that line circle surrounds is at right lower quadrant.
Figure 20 is that the SEM on the surface of the silicon substrate obtained by the etch processes of embodiment 25 is schemed
Picture.Wherein, Tu20Zhong, observes in the operation 3 of the graphical representation embodiment 25 of upper left quarter
The SEM image of silicon substrate, the graphical representation embodiment 25 of upper right quarter and right lower quadrant
The SEM image of the silicon substrate observed in operation 7.Further, by upper right quarter image with
The amplification graphical representation of the part that broken circle surrounds is at right lower quadrant.
Detailed description of the invention
Hereinafter, the present invention is described in detail.
1. etch processes compositions
The etch processes compositions of the present invention contains nitrogenous aromatic heterocyclic compounds and fluohydric acid gas.
It should be noted that the most sometimes the etch processes compositions of the present invention to be recited as " this
The compositions of invention ".
The nitrogenous aromatic heterocyclic compounds used in the present invention is that to have at least 1 nitrogen in ring former
The heterocyclic compound of son shows the compound of aromatic series.
As the nitrogenous aromatic heterocyclic compounds used in the present invention, it is possible to enumerate pyrroles, pyrrole
Azoles, imidazoles, triazole, their 5 membered ring compounds such as derivant；Pyridine, pyridazine, pyrazine,
Pyrimidine, triazine, their 6 membered ring compounds such as derivant；Indole, purine, quinoline, different
Quinoline, quinoxaline, cinnolines, quinazoline, phthalazines, naphthyridines, pteridine, acridine, naphthazine,
Azophenlyene, phenanthroline, their heterocyclic compound etc. such as derivant.Wherein, preferably pyridine or its
Derivant.As pyridine or derivatives thereof, the preferably compound shown in following formula (1):
[in above-mentioned formula (1), adjacent R1And R2、R2And R3、R3And R4Or R4With
R5Can connect and form-CR6=CR7-CR8=CR9-, R1、R2、R3、R4、R5、
R6、R7、R8, and R9Represent: hydrogen atom identical or differently；Halogen atom；Nitro；Hydroxyl
Base；Cyano group；Carbamoyl；Can have selected from halogen atom, hydroxyl, carbon number 1～
The alkoxyl of 5, the aryloxy group of carbon number 6～10, acyl group (the alkane acyl of carbon number 2～5
Base etc.), the acyloxy (alkanoyloxy etc.) of carbon number 2～5 and carbon number 6～10
The alkyl of the carbon number 1～15 of at least one substituent group in aryl；Can have selected from halogen
The carbon number 1～15 of at least one substituent group in the aryl of element atom and carbon number 6～10
Thiazolinyl；Can have at least 1 in the aryl of halogen atom and carbon number 6～10
Plant the alkynyl of the carbon number 1～15 of substituent group；Can have selected from halogen atom and carbon atom
The aryl of the carbon number 6～15 of at least one substituent group in the alkyl of several 1～5；Can have
There is the acyl group (alkanoyl etc.) of the carbon number 1～15 of at least one halogen atom substituent；Can
To have at least one substituent group in the aryl of halogen atom and carbon number 6～10
The alkoxy carbonyl group of carbon number 2～15；Can have selected from halogen atom and carbon number 1～5
Alkyl in the aryloxy carbonyl of carbon number 7～15 of at least one substituent group；Can have
The carbon atom of at least one substituent group in the aryl of halogen atom and carbon number 6～10
The alkyl sulphonyl of several 1～15；Can have selected from halogen atom and the alkane of carbon number 1～5
The aryl sulfonyl of the carbon number 6～15 of at least one substituent group in base；Can have choosing
The carbon number of at least one substituent group in the aryl of halogen atom and carbon number 6～10
The alkyl sulphinyl of 1～15；Can have selected from halogen atom and the alkane of carbon number 1～5
The aryl sulfonyl kia of the carbon number 6～15 of at least one substituent group in base；Can have
The carbon atom of at least one substituent group in the aryl of halogen atom and carbon number 6～10
The alkoxyl of several 1～15；Can have in the alkyl of halogen atom and carbon number 1～5
The aryloxy group of carbon number 6～15 of at least one substituent group；Can have at least one halogen
The acyloxy (alkanoyloxy etc.) of the carbon number 1～15 of element replacing group；Can have to
The acyl sulfenyl (alkane acyl sulfenyl etc.) of the carbon number 1～15 of few a kind of halogen atom substituent；Can
To have at least one substituent group in the aryl of halogen atom and carbon number 6～10
The alkane sulfonyl oxy of carbon number 1～15；Can have selected from halogen atom and carbon number
The aryl-sulfonyl oxygen of the carbon number 6～15 of at least one substituent group in the alkyl of 1～5；
Can have in the alkyl of carbon number 1～5 and the aryl of carbon number 6～10 at least
The carbamoyl of a kind of substituent group；Can have acyl group (the alkane acyl selected from carbon number 1～5
Base etc.) and halogen atom in the amino of at least one substituent group；Can have selected from halogen former
At least one in the alkyl of son, the aryl of carbon number 6～10 and carbon number 1～5 replaces
The N-alkyl pyridine alkali of the carbon number 6～15 of base；Can have selected from halogen atom, carbon
The carbon of at least one substituent group in the aryl of atomic number 6～10 and the alkyl of carbon number 1～5
The N-aryl-pyridine alkali of atomic number 11～15；Or organic polymer chain.]；More preferably following formula
(2) compound shown in:
[in above-mentioned formula (2), R1a、R2a、R3a、R4aAnd R5aRepresent identical or differently:
Hydrogen atom, the alkyl of carbon number 1～4, the haloalkyl of carbon number 1～4, halogen are former
Son, can have methyl or the phenyl of halogenic substituent, the alkoxyl of carbon number 1～4, carbon
The acyl group (alkanoyl etc.) of atomic number 2～4, the acyloxy (alkanoyloxy of carbon number 2～4
Deng), alkoxy carbonyl group, cyano group or the nitro of carbon number 2～4.]；Particularly preferred: pyridine,
2-picoline, 3-picoline, 4-picoline, 2,4-lutidines, 2,5-dimethyl pyrazole
Pyridine, 2,6-lutidines, 3,4-lutidines, 3,5-lutidines, 3,6-dimethyl pyrazole
Pyridine, 2-chloropyridine, 3-chloropyridine, 4-chloropyridine, 2,4-dichloropyridine, 2,5-dichloropyridine, 2,6-
Dichloropyridine, 3,4-dichloropyridine, 3,5-dichloropyridine, 3,6-dichloropyridine.
Nitrogenous aromatic heterocyclic compounds included in the compositions of the present invention both can individually make
With a kind, can be applied in combination two or more.When being applied in combination two or more, by above-mentioned nitrogenous
Aromatic heterocyclic compounds carries out combination in any, and its ratio of components is not particularly limited.
For the content of the nitrogenous aromatic heterocyclic compounds in the compositions of the present invention, as long as
It is the scope that can compatibly be etched processing, is then not particularly limited, with total composition
On the basis of, usually 0.01～about 100mol/L, preferably 0.1～about 50mol/L, more
It is preferably 1～25mol/L.
The fluohydric acid gas used in the present invention is preferably with the form (fluorination hydracid or Fluohydric acid .) of aqueous solution
Use.Hydrogen fluoride concentration in this aqueous solution is not particularly limited, and usually 0.1～about 80%,
It is preferably 1～about 40%.And, it is also possible in this aqueous solution, add solvable solvent.Make
For this solvent, such as, can enumerate methanol, ethanol, propanol, ethylene glycol etc..
For the content of the fluohydric acid gas in the compositions of the present invention, as long as can compatibly enter
The scope of row etch processes, then be not particularly limited, on the basis of total composition, be 0.001～
About 200mol/L, preferably 0.01～about 100mol/L, more preferably 0.1～50mol/L.
Further, the nitrogenous aromatic heterocyclic compounds in the compositions of the present invention and the group of fluohydric acid gas
Become ratio, as long as the scope processed can be compatibly etched, be then not particularly limited, excellent
Choosing (nitrogenous aromatic heterocyclic compounds fluohydric acid gas) molar concentration rate be (100 1)～
(1 200) left and right, more preferably (50 1)～(1 100) left and right, further preferably
(10 1)～(1 50) left and right, particularly preferably (1 10)～(1 25) left and right.
The compositions of the present invention can also contain oxidant.This of oxidant is contained by use
Bright compositions, it is possible to increase etch processes speed, it is possible to form gold word in shorter time
The texture of turriform shape.
As oxidant, as long as electronics can be accepted from the treated object of etch processes, and can
Oxidation treated object surface, then be not particularly limited, from operation ease and the sight becoming present aspect
Point sets out, preferably hydrogen peroxide, peracetic acid, the oxidation of above-mentioned nitrogenous aromatic heterocyclic compounds
Thing, ozone, sulphuric acid or nitric acid, the most more preferably hydrogen peroxide or above-mentioned nitrogenous heteroaromatic
The oxide of compound.
Hydrogen peroxide preferably uses with the form (aquae hydrogenii dioxidi) of aqueous solution.In this aqueous solution
The concentration of hydrogen peroxide be not particularly limited, be 0.01～about 100mol/L, be preferably
0.01～about 50mol/L, more preferably 0.1～about 25mol/L.
The oxide of nitrogen-containing heterocycle compound is to combine aerobic at least 1 nitrogen-atoms in ring
The compound of atom, specifically, is to have the part structure shown in following formula (3) in ring
Compound.
Compound as the part structure having shown in above-mentioned formula (3), it is possible to enumerate pyridine-n-
Oxide, pyridazine-n-oxide, pyridazine-1,2-dioxide, pyrazine-n-oxide, pyrazine-1,4-
Dioxide, pyrimidine-n-oxide, pyrimidine-1,3-dioxide, their derivant etc. 6 yuan
Cycle compound.Wherein, the preferred compound shown in following formula (4):
[in above-mentioned formula (4), adjacent R1And R2、R2And R3、R3And R4Or R4With
R5Can connect and form-CR6=CR7-CR8=CR9-, R1、R2、R3、R4、R5、
R6、R7、R8, and R9Represent: hydrogen atom identical or differently；Halogen atom；Nitro；Hydroxyl
Base；Cyano group；Carbamoyl；Can have selected from halogen atom, hydroxyl, carbon number 1～
The alkoxyl of 5, the aryloxy group of carbon number 6～10, acyl group (the alkane acyl of carbon number 2～5
Base etc.), the acyloxy (alkanoyloxy etc.) of carbon number 2～5 and carbon number 6～10
The alkyl of the carbon number 1～15 of at least one substituent group in aryl；Can have selected from halogen
The carbon number 1～15 of at least one substituent group in the aryl of element atom and carbon number 6～10
Thiazolinyl；Can have at least 1 in the aryl of halogen atom and carbon number 6～10
Plant the alkynyl of the carbon number 1～15 of substituent group；Can have selected from halogen atom and carbon atom
The aryl of the carbon number 6～15 of at least one substituent group in the alkyl of several 1～5；Can have
There is the acyl group (alkanoyl etc.) of the carbon number 1～15 of at least one halogen atom substituent；Can
To have at least one substituent group in the aryl of halogen atom and carbon number 6～10
The alkoxy carbonyl group of carbon number 2～15；Can have selected from halogen atom and carbon number 1～5
Alkyl in the aryloxy carbonyl of carbon number 7～15 of at least one substituent group；Can have
The carbon atom of at least one substituent group in the aryl of halogen atom and carbon number 6～10
The alkyl sulphonyl of several 1～15；Can have selected from halogen atom and the alkane of carbon number 1～5
The aryl sulfonyl of the carbon number 6～15 of at least one substituent group in base；Can have choosing
The carbon number of at least one substituent group in the aryl of halogen atom and carbon number 6～10
The alkyl sulphinyl of 1～15；Can have selected from halogen atom and the alkane of carbon number 1～5
The aryl sulfonyl kia of the carbon number 6～15 of at least one substituent group in base；Can have
The carbon atom of at least one substituent group in the aryl of halogen atom and carbon number 6～10
The alkoxyl of several 1～15；Can have in the alkyl of halogen atom and carbon number 1～5
The aryloxy group of carbon number 6～15 of at least one substituent group；Can have at least one halogen
The acyloxy (alkanoyloxy etc.) of the carbon number 1～15 of element replacing group；Can have to
The acyl sulfenyl (alkane acyl sulfenyl etc.) of the carbon number 1～15 of few a kind of halogen atom substituent；Can
To have at least one substituent group in the aryl of halogen atom and carbon number 6～10
The alkane sulfonyl oxy of carbon number 1～15；Can have selected from halogen atom and carbon number
The aryl-sulfonyl oxygen of the carbon number 6～15 of at least one substituent group in the alkyl of 1～5；
Can have in the alkyl of carbon number 1～5 and the aryl of carbon number 6～10 at least
The carbamoyl of a kind of substituent group；Can have acyl group (the alkane acyl selected from carbon number 1～5
Base etc.) and halogen atom in the amino of at least one substituent group；Can have selected from halogen former
At least one in the alkyl of son, the aryl of carbon number 6～10 and carbon number 1～5 replaces
The N-alkyl pyridine alkali of the carbon number 6～15 of base；Can have selected from halogen atom, carbon
The carbon of at least one substituent group in the aryl of atomic number 6～10 and the alkyl of carbon number 1～5
The N-aryl-pyridine alkali of atomic number 11～15；Or organic polymer chain.]；More preferably following formula
(5) compound shown in:
[in above-mentioned formula (5), R1a、R2a、R3a、R4aAnd R5aRepresent identical or differently:
Hydrogen atom, the alkyl of carbon number 1～4, the haloalkyl of carbon number 1～4, halogen are former
Son, can have methyl or the phenyl of halogenic substituent, the alkoxyl of carbon number 1～4, carbon
The acyl group (alkanoyl etc.) of atomic number 2～4, the acyloxy (alkanoyloxy of carbon number 2～4
Deng), alkoxy carbonyl group, cyano group or the nitro of carbon number 2～4.]；Particularly preferred: 2-methyl pyrrole
Pyridine-N-oxide, 3-methylpyridine N oxide, 4-methylpyridine N oxide, 2,4-diformazan
Pyridine-N-oxide, 2,5-dimethylpyridine-N-oxide, 2,6-lutidines-N-aoxidize
Thing, 3,4-dimethylpyridine-N-oxide, 3,5-dimethylpyridine-N-oxide, 3,6-dimethyl
Pyridine-N-oxides, 2-chloropyridine-N-oxide, 3-chloropyridine-N-oxide, 4-chloropyridine-N-
Oxide, 2,4-dichloropyridine-N-oxide, 2,5-dichloropyridine-N-oxide, 2,6-dichloro pyrrole
Pyridine-N-oxide, 3,4-dichloropyridine-N-oxide, 3,5-dichloropyridine-N-oxide, 3,6-
Dichloropyridine-N-oxide.
When the compositions of the present invention contains oxidant, the present invention as long as its content will not significantly detract
Effect, then be not particularly limited, on the basis of total composition, usually 0.001～
About 200mol/L, preferably 0.01～about 100mol/L, more preferably 0.1～50mol/L.
Further, when the compositions of the present invention contains oxidant, fluohydric acid gas and the ratio of components of oxidant,
So long as not the effect of the notable present invention that detracts, then it is not particularly limited, (fluohydric acid gas oxidant)
Molar concentration rate be preferably (50 1)～(1 50) left and right, more preferably (20 1)～
(1 20) left and right, further preferably (10 1)～(1 10) left and right, particularly preferably (5
1)～(1 5) left and right.
During additionally, the compositions of the present invention contains oxidant, nitrogenous aromatic heterocyclic compounds with
Fluohydric acid gas and the ratio of components of oxidant, as long as the effect of the present invention that will not significantly detract, then do not have
Particular restriction, the molar concentration rate of (nitrogenous aromatic heterocyclic compounds fluohydric acid gas and oxidant)
It is preferably (100 1)～(1 100) left and right, more preferably (50 1)～(1 50)
Left and right, further preferably (20 1)～(1 20) left and right, particularly preferably (10 1)～
(1 10) left and right.
For the form of the compositions of the present invention, as long as can be with when being etched and processing
The form of treated object contact, then be not particularly limited, from the easy degree of the modulation of compositions
From the viewpoint of operation ease, preferably liquid.Solvent is not particularly limited, such as
Water etc. can be used.
Additionally, the modulator approach for the compositions of the present invention is not particularly limited, such as, energy
Enough methods by adding nitrogenous aromatic heterocyclic compounds in aqueous hydrogen fluoride solution etc. and modulate.
2. etching processing method
The etching processing method of the present invention includes: (1) makes above-mentioned etch processes compositions and quilt
The operation of processed material contact.It should be noted that the most sometimes this operation is recited as " work
Sequence (1) ".
As treated object, it is possible to enumerate the solid material such as semi-conducting material, insulating material.
As semi-conducting material, such as can enumerate silicon (monocrystal silicon, polysilicon, non-crystalline silicon etc.), germanium,
SiGe, carborundum (SiC), GaAs, aluminum gallium arsenide, indium phosphide, indium antimonide, gallium nitride,
Aluminium nitride etc..Additionally, as insulating material, such as can enumerate zirconium oxide, hafnium oxide,
The metal-oxides such as tantalum oxide, aluminium oxide, titanium oxide, chromium oxide and their silicate, two
The Si oxide such as silicon oxide, quartz, silicon nitride, sapphire etc..
It addition, the surface configuration etc. about treated object is not particularly limited, such as, to being located
Whole faces of reason thing implement mirror process situation, only to the one side of treated object (such as this
The contact surface of the compositions of invention) implement the situation of mirror process, do not implement mirror process
Situation etc., all can be preferably used.As a example by silicon materials, as implementing mirror process
Situation can enumerate LSI silicon substrate, can enumerate as the situation not implementing mirror process
Silicon for solar cell substrate.
Further, treated object can be the material implementing pre-treatment before operation (1).Make
For pre-treatment, it is possible to enumerate the mixing by acetone and other organic solvent, sulphuric acid and aquae hydrogenii dioxidi
The organic process on the treated object surfaces such as thing；Removed by Fluohydric acid. or buffered hydrofluoric acid etc.
The process of the oxide-film on treated object surface；By hydrochloric acid, nitric acid and the mixing of aquae hydrogenii dioxidi
Things etc. remove the process etc. of metal impurities.
For silicon for solar cell substrate, generally cut by free abrasive particle or bonded-abrasive
Silicon, and do not carry out mirror process.Particularly in the situation of monocrystalline silicon substrate used for solar batteries
Under, cut along (100) face generally, due to silicon, there is cutting edge at this substrate surface and collapse
Vestige caused by Kou.This vestige caused by cutting edge chipping can become the starting point of etching, therefore,
When being etched processing as treated object using this material, it is possible to formed in shorter time
The texture of inverted pyramid shape.
For the method making the compositions of the present invention contact with treated object, it is not particularly limited,
It is made to contact by known method.For instance, it is possible to by the tape casting, spin-coating method, spray
Cloth methods such as coating, ink-jet method, scraper for coating method or treated object is immersed in the present invention's
Compositions is implemented.
The compositions of the present invention, both can be to whole faces of treated object to the contact of treated object
Carry out, can carry out at the site portion desired by treated object.By the combination of the present invention
Thing carries out situation about contacting with whole faces of treated object, it is possible to enter whole faces of treated object
Row etching, carries out part contact by the compositions of the present invention with the position desired by treated object
Situation, it is possible to only the contact surface of the compositions of the present invention is partially etched.It addition, cover
After covering, method or the ink-jet method of spraying can make the compositions of the present invention and the desired of treated object
Site portion contact, thus preferably.
Additionally, treated object can be by the etch processes side of the present invention before operation (1)
Method beyond method is carried out the material that overetch processes.Etching processing method as the present invention
Method in addition, such as, can enumerate the erosion that alkali etching processes or above-mentioned patent documentation 1 is recorded
Process at quarter etc..
Additionally, the etching processing method of the present invention also includes the work of (2-1) heating treated object
Sequence.It should be noted that the most sometimes this operation to be recited as " operation (2-1) ".
As long as the temperature that heating-up temperature exceedes room temperature (about 20 DEG C) is then not particularly limited,
Preferably more than 25 DEG C, more preferably more than 60 DEG C, further preferred more than 75 DEG C.Wherein, adding
Carry out during aftermentioned operation (2-2) preferably more than 25 DEG C while heat, do not carry out aftermentioned operation (2
-2) time preferably more than 28 DEG C.Arbitrary when when carrying out aftermentioned operation (2-2) and not carrying out
In the case of Zhong, as long as heating-up temperature to be set to more than 60 DEG C (preferably more than 75 DEG C, more preferably 150 DEG C
Above), it becomes possible to improve etch processes speed further.The higher limit of heating-up temperature is the most special
Limiting, but be preferably, each composition included in the compositions of the present invention carries out the temperature decomposed
Below degree.Specifically, preferably less than 200 DEG C, more preferably less than 150 DEG C.
Heat time heating time is also not particularly limited, according to formed by desired etch processes
Set to the suitable size of the texture of inverted pyramid shape.Specifically, preferably 1 point～2
About hour.Thereby, it is possible to form gold word the most expeditiously on the surface of treated object
The texture of turriform shape.Wherein, heating-up temperature less than 60 DEG C time more preferably 5 points～about 2 hours,
When heating-up temperature is more than 60 DEG C more preferably about 1～30 point.It addition, enter while heating
During row aftermentioned operation (2-2), the state of the process of irradiation energy line preferably heating.
Heating means are also not particularly limited, and can use the method in the past carried out.Such as, energy
Enough use heating plate, Peltier's element, water-bath, oil bath, temperature chamber, constant temperature and humidity cabinet, do
Dry machine, calorstat (incubator), heating furnace, electric furnace, infrared ray radiation etc..
By this operation (2-1), it is possible in treated object, the compositions with the present invention contacts
Whole faces in face, improve etch processes speed.
Additionally, in the etching processing method of the present invention, above-mentioned operation both can have been carried out in order
(1) carry out operation (2-1) after, above-mentioned operation (1) and operation (2 can be carried out simultaneously
-1).As carrying out operation (1) and the method for operation (2-1) simultaneously, such as, can enumerate:
It is redefined for above-mentioned heating-up temperature, by treated object by heating etch processes compositions
In this heated compositions, impregnate the time identical with above-mentioned heat time heating time and be brought into contact with
Method etc..By so carrying out operation (1) and operation (2-1) simultaneously, it is possible to reduce etching
Workload needed for process.
It addition, might not be clear by adding thermally-induced reaction mechanism, but if with processed
In case of thing is silicon it is considered to be: risen by the temperature on treated object surface, nitrogenous
Electronic receipt between aromatic heterocyclic compounds and silicon comes to life, and silicon is fluorinated at interface,
Promote etch processes therefrom.It addition, in high temperature (specially more than 60 DEG C), the present invention
Compositions viscosity decline, become easily to flow, therefore silicon face always can with activity contain
Nitrogen aromatic heterocyclic compounds contacts.
Additionally, the etching processing method of the present invention also includes: (2-2) treated object with erosion
Carve the operation of irradiation energy line on the face of composition for treating contact.It should be noted that under
Sometimes this operation is recited as in asking " operation (2-2) ".
As the energy line irradiated, as long as electron excitation can be caused in treated object, then do not have
There is particular restriction, such as, can enumerate visible ray, ultraviolet, infrared ray, X-ray, electronics
Bundle, ion beam, laser beam etc..Wherein, preferably visible ray or ultraviolet.
It should be noted that wherein, it is seen that the wavelength of light is 400～about 800nm, ultraviolet
Wavelength be 10～about 400nm, ultrared wavelength is 800nm～about 25 μm, and X penetrates
The wavelength of line is 0.01～about 70nm, and the accelerating potential of electron beam is 0.1kV～200kV is left
The right side, the accelerating potential of ion beam is 1kV～about 200kV.Additionally, laser beam is because of can be accurate
Really and easily control the range of exposures of light and excellent, it is possible to not by pulse width, output, ripple
Long, mode of oscillation and the restriction of medium and use.Additionally, as can irradiate have visible ray～
The energy line source of the energy line of the wavelength of ultraviolet range, such as, can use xenon lamp.
For the irradiation condition of energy line, as long as can compatibly be etched processing, then do not have
There is particular restriction.Such as, as exposure rate, it is possible to 0.001～10W/cm2Left and right, excellent
Choosing is with 0.1～5W/cm2Left and right, as irradiation time, it is possible to 1 second～about 2 hours, excellent
Choosing is carried out with the condition of 10 seconds～about 2 hours.
During irradiation energy line, the face that both compositions with the present invention of treated object can have been contacted
Whole faces be irradiated, it is also possible to by carrying out the method sheltered or utilizing the parts such as spotlight
Ground is to the position irradiation energy line desired by treated object.
By this operation (2-2), it is possible to throughout whole faces of energy line shadow surface, improve etching
Processing speed.
Additionally, in the etching processing method of the present invention, above-mentioned operation both can have been carried out in order
(1) carry out operation (2-2) after, above-mentioned operation (1) and operation (2 can be carried out simultaneously
-2).As carrying out operation (1) and the method for operation (2-2) simultaneously, such as, can enumerate:
Energy line at xenon lamp etc. irradiates under environment, by treated object in etch processes compositions
The method etc. impregnating the time identical with the irradiation time of above-mentioned energy line and be brought into contact with.Pass through
Carry out operation (1) and operation (2-2), it is possible to reduce the work needed for etch processes the most simultaneously
Measure.
Additionally, in the etching processing method of the application, above-mentioned operation both can have been carried out in order
(1), after, carry out above-mentioned operation (2-1), carry out operation (2-2) afterwards；Can carry out
After above-mentioned operation (1), carry out above-mentioned operation (2-1) and operation (2-2) simultaneously；Also may be used
To carry out above-mentioned operation (1), operation (2-1) and operation (2-2) simultaneously.
After carrying out operation (1), carry out above-mentioned operation (2-1) and operation (2-2) simultaneously
Method, such as can enumerate: etch processes compositions is coated treated object and makes it
After contact, by first-class for this treated object heating plate under the energy line irradiation environment of xenon lamp etc.
Stand the irradiation time of above-mentioned heat time heating time and/or energy line, carry out simultaneously energy line irradiate and
The method etc. of heating.By so carrying out operation (2-1) and operation (2-2), not only simultaneously
The workload needed for etch processes can be reduced, additionally it is possible to more improve etch processes speed.
As carrying out operation (1), operation (2-1) and the method for operation (2-2) simultaneously,
Such as can enumerate: be redefined for above-mentioned heating temperature by heating etch processes compositions
Degree, the energy line at xenon lamp etc. irradiates under environment, by treated object in this heated combination
Thing impregnates the time identical with above-mentioned heat time heating time and/or energy line irradiation time and is allowed to connect
The method etc. touched.By so carrying out operation (1), operation (2-1) and operation (2-simultaneously
2), it is possible to workload etch processes needed for is greatly reduced, and then etch processes can be improved
Speed, the most preferably.
And then, in the etching processing method of the present invention, after above-mentioned operation, it is also possible to bag
Include: the residue of the compositions of the present invention with treated object is removed from treated object by (3) simultaneously
Operation.
As the method that the compositions of the present invention is removed from treated object, as long as can remove
It is attached to etch processes compositions and the etch residue of treated object, is then not particularly limited,
Such as can enumerate: treated object be impregnated in water or the method for water-miscible organic solvent, Bian Xuan
Turn the method etc. that treated object is jetted by limit.
3. etch processes thing
The treated object obtained by the etching processing method of the invention described above (below, is remembered sometimes
Carry as " the etch processes thing of the present invention ".), there is the texture of inverted pyramid shape on its surface.
Wherein, so-called " texture of inverted pyramid shape ", refer to be etched the processed of process
Thing surface with inverted pyramid (rectangular pyramid) bottom surface and the recess of the shape etch on summit.
It addition, for the texture of inverted pyramid shape, as long as it is capable of identify that as being equivalent to pyramid
The recess minimum point on summit and be equivalent to the shape of point on summit, pyramidal bottom surface, no
Requirement must be Pyramid completely.Such as, the recess being equivalent to pyramid summit is minimum
Point with arc can also, bottom surface be shaped as the most polygon-shaped or roundish shape can also.
The degree of depth of the texture of the inverted pyramid shape that the etch processes thing of the present invention is had is (i.e.,
Pyramidal height) it is preferably about 1nm～50 μm, about more preferably 10nm～20 μm.
Time as a example by silicon substrate, the degree of depth of the texture of inverted pyramid shape is the erosion of scope as above
Carve processed material, preferred because of the antiradar reflectivity of its light and/or sunken light effect height.It addition, fall
The degree of depth of the texture of Pyramid such as can be passed through sweep electron microscope (SEM) and see
Examine etc. and measure.
The diameter of the texture of the inverted pyramid shape that the etch processes thing of the present invention is had is (i.e.,
Pyramidal bottom surface is considered as the average diameter of bowlder) it is preferably about 10nm～50 μm, more
It is preferably about 50nm～20 μm.Time as a example by silicon substrate, the texture of inverted pyramid shape
The etch processes thing of a diameter of scope as above, because of its light antiradar reflectivity and/or fall into
Light effect is high and preferred.It addition, the diameter of the texture of inverted pyramid shape such as can be by sweeping
Retouch formula ultramicroscope (SEM) observation to wait and measure.
As it has been described above, the etch processes thing of the present invention with the texture of inverted pyramid shape has very
The antiradar reflectivity of high light and/or sunken light effect.Thus, the etch processes thing of the present invention is made
It is useful for material used for solar batteries.And then, comprise the etch processes thing of the present invention too
Sun can be capable of high conversion efficiency by battery.
Further, by before the operation (1) of the etching processing method in the invention described above beforehand through
Method beyond etching processing method of the present invention carries out the object of overetch process as treated object
Time, the etch processes thing of the present invention has dual texture.As a example by silicon substrate, it is known that in operation
(1) front carry out parlkaline etch processes in the case of, this silicon substrate formed pyramid
The texture of shape.When this silicon substrate is used as treated object, obtained etch processes thing
There is dual texture, i.e. in the side of this Pyramid (main texture), formation results from
Minute aperture (secondary texture) to the triangular prism shape of the anisotropic etching in (111) face.
Additionally, time as a example by the silicon substrate that (100) show out, it is known that advance in operation (1)
In the case of the etching processing method that above-mentioned patent documentation 1 of going is recorded, should be eclipsed in (100) face
Carve, form the texture of inverted pyramid shape.When this silicon substrate is used as treated object,
The etch processes thing obtained has dual texture, i.e. at this inverted pyramid shape (main texture)
Side, form the elongated ditch of the transverse direction of anisotropic etching resulted to (110) face
(secondary texture).
The etch processes thing of the present invention as mentioned above with dual texture it is believed that the low reflection of light
Rate and/or sunken light effect uprise.
Embodiment
Below, enumerate embodiment and further describe the present invention, but the present invention does not limit
Due to following example.
It should be noted that in the examples below, make as nitrogenous aromatic heterocyclic compounds
With the pyridine solution of 12.4mol/L, use the Fluohydric acid. of 28.75mol/L as fluohydric acid gas.
Additionally, in embodiment 17～22, use the hydrogen peroxide of 9.794mol/L as hydrogen peroxide
Water, and in embodiment 23 and 24, use the pyridine-N-oxides of 10.29mol/L.
Additionally, as treated object and energy line irradiation source, use following material.
< treated object ＞
Silicon for solar cell substrate (N-shaped, planar orientation (100), resistivity: 0.5～3.5 Ω
Cm, thickness: 200 μm, it is that therefore surface has small with the silicon substrate of free abrasive particle cutting
The vestige caused by cutting edge chipping).It should be noted that in the examples below, this sun
" silicon substrate " can be made by battery silicon substrate brief note.Additionally, in the present embodiment, this silicon substrate
Carried out the most in advance being removed organic process by acetone and being removed oxide skin by Fluohydric acid.
The process of film.
< energy line irradiation source ＞
Xenon lamp (output: 150W, through wavelength: 220～2000nm, activity: 2 μm/cm2
·nm-1)。
Embodiment 1
< operation 1: the cloth ＞ of etch processes compositions
With 1 12 (molar concentration rate) mixing pyridine and Fluohydric acid., 125 μ L etchings are modulated
Composition for treating, then that this etch processes compositions is square with 5mm on a silicon substrate
It is thick that scope is coated into 5mm.
< operation 2: the temperature of silicon substrate controls ＞
In the heating plate of band refrigerating function, it is placed through the silicon substrate that above-mentioned operation 1 obtains,
After plate temperature is set as 100 DEG C, as shown in Figure 1 silicon substrate is placed 15 minutes in darkroom.
It addition, use the surface temperature of temperature sensor measurement silicon substrate, confirm the silicon substrate in experiment
Surface temperature identical with setting.
< operation 3: the SEM of silicon substrate observes ＞
By the etch processes compositions on the silicon substrate experiencing above-mentioned operation 2 with by etch processes
After the residue produced removes, observed the table of silicon substrate by sweep electron microscope (SEM)
Face and cross sectional shape.The SEM image in silicon substrate and cross section is represented in fig. 2.
Embodiment 2
In the operation 2 of embodiment 1, by silicon substrate darkroom placement 20 minutes, in addition,
Operate similarly to Example 1 and carry out the etch processes of silicon substrate.By silicon substrate and cross section
SEM image represent in figure 3.
Embodiment 3
In the operation 2 of embodiment 1, by silicon substrate darkroom placement 25 minutes, in addition,
Operate similarly to Example 1 and carry out the etch processes of silicon substrate.By silicon substrate and cross section
SEM image represent in the diagram.
The SEM image of the silicon substrate obtained with the etch processes of embodiment 1～3 (is schemed
2～4) carry out arranging and representing in Figure 5.Wherein, in Fig. 5, reference example 1 represents etching
The SEM image of silicon substrate before treatment, reference example 2 represents: in the operation of embodiment 1
In 2, by silicon substrate darkroom place 10 minutes, the most similarly to Example 1 operation and
It is etched the SEM image of the silicon substrate processed.
As can be seen from Figure 5, when being etched processing in darkroom, from placing under darkroom 10
About minute, gradually proceed by etch processes, at about 15 minutes, in silicon substrate shape
Become minute aperture, initially form the texture of inverted pyramid shape at about 20 minutes, at 25 minutes
Left and right forms the texture of inverted pyramid shape.
Embodiment 4
< operation 1: the cloth ＞ of etch processes compositions
With 1 12 (molar concentration rate) mixing pyridine and Fluohydric acid., obtain at 125 μ L etchings
Reason compositions, then by this etch processes compositions on a silicon substrate with model that 5mm is square
Enclose and be coated into 5mm thickness.
< operation 2: the temperature of silicon substrate controls ＞
In the heating plate of band refrigerating function, it is placed through the silicon substrate that above-mentioned operation 1 obtains,
Plate temperature is set as 100 DEG C.
< operation 3: the irradiation ＞ of energy line
Use the surface temperature of temperature sensor measurement silicon substrate, the silicon substrate in confirmation experiment
After surface temperature is identical with setting, as shown in Figure 6, this silicon substrate is irradiated xenon lamp (to expose
Optical wavelength: 220～2000nm, exposure intensity: 1.5W/cm2) 3 minutes.
< operation 4: the SEM of silicon substrate observes ＞
By the etch processes compositions on the silicon substrate experiencing above-mentioned operation 3 with by etch processes
After the residue produced removes, observed the table of silicon substrate by sweep electron microscope (SEM)
Face shape.The SEM image of silicon substrate is represented in the figure 7.
Embodiment 5
In the operation 3 of embodiment 4, the irradiation time of xenon lamp is set to 5 minutes, except this
In addition, operate similarly to Example 4 and carry out the etch processes of silicon substrate.By silicon substrate
SEM image represent in fig. 8.
Embodiment 6
In the operation 3 of embodiment 4, the irradiation time of xenon lamp is set to 8 minutes, except this
Outside, operate similarly to Example 4 and carry out the etch processes of silicon substrate.By silicon substrate
SEM image represent in fig .9.
Embodiment 7
In the operation 3 of embodiment 4, the exposure intensity of xenon lamp is set to 2.5W/cm2, remove
Outside this, operate similarly to Example 4 and carry out the etch processes of silicon substrate.By silicon substrate table
The SEM image in face represents in Fig. 10.
Embodiment 8
In the operation 3 of embodiment 4, the exposure intensity of xenon lamp is set to 2.5W/cm2, and
The irradiation time of xenon lamp is set to 5 minutes, in addition, similarly to Example 4 operation and
Carry out the etch processes of silicon substrate.The SEM image of silicon substrate is represented in fig. 11.
Embodiment 9
In the operation 3 of embodiment 4, the exposure intensity of xenon lamp is set to 2.5W/cm2, and
The irradiation time of xenon lamp is set to 8 minutes, in addition, similarly to Example 4 operation and
Carry out the etch processes of silicon substrate.The SEM image of silicon substrate is represented in fig. 12.
Embodiment 10
In the operation 3 of embodiment 4, the exposure intensity of xenon lamp is set to 3.5W/cm2, remove
Outside this, operate similarly to Example 4 and carry out the etch processes of silicon substrate.By silicon substrate table
The SEM image in face represents in fig. 13.
Embodiment 11
In the operation 3 of embodiment 4, the exposure intensity of xenon lamp is set to 3.5W/cm2, and
The irradiation time of xenon lamp is set to 5 minutes, in addition, similarly to Example 4 operation and
Carry out the etch processes of silicon substrate.The SEM image of silicon substrate is represented in fig. 14.
As knowable to Fig. 2～14, suggest along with the exposure intensity of xenon lamp becomes strong, to being formed
The time of the texture of inverted pyramid shape shortens.
Embodiment 12
In the operation 1 of embodiment 4, use pyridine and Fluohydric acid. with 12 1 (molar concentrations
Than) carry out the etch processes compositions that mixes, and by xenon in the operation 3 of embodiment 4
The exposure intensity of gas lamp is set to 2.5W/cm2, in addition, operate similarly to Example 4 and enter
The etch processes of row silicon substrate.
Embodiment 13
In the operation 1 of embodiment 4, use pyridine and Fluohydric acid. with 12 1 (molar concentrations
Than) carry out the etch processes compositions that mixes, and by xenon in the operation 3 of embodiment 4
The exposure intensity of gas lamp is set to 2.5W/cm2, and the irradiation time of xenon lamp is set to 5 minutes,
In addition, operate similarly to Example 4 and carry out the etch processes of silicon substrate.
Embodiment 14
In the operation 1 of embodiment 4, use pyridine and Fluohydric acid. with 1 23 (molar concentrations
Than) carry out the etch processes compositions that mixes, and by xenon in the operation 3 of embodiment 4
The exposure intensity of gas lamp is set to 2.5W/cm2, in addition, operate similarly to Example 4 and enter
The etch processes of row silicon substrate.
Embodiment 15
In the operation 1 of embodiment 4, use pyridine and Fluohydric acid. with 1 23 (molar concentrations
Than) carry out the etch processes compositions that mixes, and by xenon in the operation 3 of embodiment 4
The exposure intensity of gas lamp is set to 2.5W/cm2, and the irradiation time of xenon lamp is set to 5 minutes,
In addition, operate similarly to Example 4 and carry out the etch processes of silicon substrate.
Embodiment 16
In the operation 1 of embodiment 4, use pyridine and Fluohydric acid. with 1 23 (molar concentrations
Than) carry out the etch processes compositions that mixes, and by xenon in the operation 3 of embodiment 4
The exposure intensity of gas lamp is set to 2.5W/cm2, and the irradiation time of xenon lamp is set to 8 minutes,
In addition, operate similarly to Example 4 and carry out the etch processes of silicon substrate.
By with embodiment 7～9 and the silicon substrate that obtains of the etch processes of embodiment 12～16
SEM image carry out arranging and representing in fig .15.Wherein, Tu15Zhong, reference example 3 table
Show the SEM image of the silicon substrate before etch processes.
Can be enlightened from Figure 15, along with the ratio of the pyridine in etch processes compositions uprises,
Time to the texture forming inverted pyramid shape shortens.
Embodiment 17
< operation 1: the cloth ＞ of etch processes compositions
With 21 16 (molar concentration rate) mixing pyridine, Fluohydric acid. and aquae hydrogenii dioxidi,
To 125 μ L etch processes compositionss, then by this etch processes by compositions on a silicon substrate
It is coated into 5mm thick with the scope that 5mm is square.
< operation 2: the temperature of silicon substrate controls ＞
In the heating plate of band refrigerating function, it is placed through the silicon substrate that above-mentioned operation 1 obtains,
Plate temperature is set as 100 DEG C.
< operation 3: the irradiation ＞ of energy line
Use the surface temperature of temperature sensor measurement silicon substrate, the silicon substrate in confirmation experiment
After surface temperature is identical with setting, as shown in figure 16, this silicon substrate is irradiated xenon lamp (to expose
Optical wavelength: 220～2000nm, exposure intensity: 2.5W/cm2) 5 minutes.
< operation 4: the SEM of silicon substrate observes ＞
By the etch processes compositions on the silicon substrate experiencing above-mentioned operation 3 with by etch processes
After the residue produced removes, observed the table of silicon substrate by sweep electron microscope (SEM)
Face shape.
Embodiment 18
In the operation 1 of embodiment 17, use pyridine, Fluohydric acid. and aquae hydrogenii dioxidi with 7
9 54 (molar concentration rates) carry out the etch processes compositions mixed, and in embodiment
In the operation 3 of 17, the irradiation time of xenon lamp is set to 10 minutes, in addition, with enforcement
Example 17 operates equally and carries out the etch processes of silicon substrate.
Embodiment 19
In the operation 1 of embodiment 17, use pyridine, Fluohydric acid. and aquae hydrogenii dioxidi with 7
18 108 (molar concentration rates) carry out the etch processes compositions mixed, and are implementing
In the operation 3 of example 17, the irradiation time of xenon lamp is set to 10 minutes, in addition, with
Embodiment 17 operates equally and carries out the etch processes of silicon substrate.
Embodiment 20
In embodiment 17 operation 2, plate temperature is set as 150 DEG C, and in embodiment 17
Operation 3 in, the irradiation time of xenon lamp is set to 2 minutes, in addition, with embodiment
17 operate equally and carry out the etch processes of silicon substrate.
Embodiment 21
In the operation 1 of embodiment 17, use pyridine, Fluohydric acid. and aquae hydrogenii dioxidi with 7
9 54 (molar concentration rates) carry out the etch processes compositions mixed, and in embodiment
In 17 operations 2, plate temperature is set as 150 DEG C, and in the operation 3 of embodiment 17, will
The irradiation time of xenon lamp is set to 15 minutes, in addition, similarly to Example 17 operation and
Carry out the etch processes of silicon substrate.
Embodiment 22
In the operation 1 of embodiment 17, use pyridine, Fluohydric acid. and aquae hydrogenii dioxidi with 7
18 108 (molar concentration rates) carry out the etch processes compositions mixed, and are implementing
In example 17 operation 2, plate temperature is set as 150 DEG C, and in the operation 3 of embodiment 17,
The irradiation time of xenon lamp is set to 10 minutes, in addition, operates similarly to Example 17
And carry out the etch processes of silicon substrate.
The SEM image of silicon substrate that will be obtained by the etch processes of embodiment 17～22
Carry out arranging and representing in fig. 17.
Embodiment 23
In the operation 1 of embodiment 17, use pyridine, Fluohydric acid. and pyridine-N-oxides
The etch processes compositions mixed is carried out, except this it with 47 559 1 (molar concentration rates)
Outward, operate similarly to Example 17 and carry out the etch processes of silicon substrate.By silicon substrate
SEM image represents in figure 18.
As can confirm that from Figure 17 and 18, by coordinating peroxidating in etch processes compositions
The oxidant of hydrogen or pyridine-N-oxides etc., it is possible to foreshorten to be formed the texture of inverted pyramid shape
Time.
Embodiment 24
< operation 1: alkali etching processes ＞
By silicon substrate is impregnated in being warmed as the potassium hydroxide aqueous solution of 20 mass % of 80 DEG C
30 minutes and carried out alkali etching process.After carrying out 2 times rinsing with ultra-pure water, by scanning
The surface configuration of silicon substrate observed by formula ultramicroscope (SEM).By the SEM image of silicon substrate
Represent in Figure 19.
< operation 2: the cloth ＞ of etch processes compositions
With 1 12 (molar concentration rate) mixing pyridine and Fluohydric acid., obtain etch processes combination
Thing, then coats the SEM observation completing above-mentioned operation 1 by this etch processes compositions
Silicon substrate on.
< operation 3: the temperature of silicon substrate controls ＞
In the heating plate of band refrigerating function, it is placed through the silicon substrate that above-mentioned operation 2 obtains,
Plate temperature is set as 100 DEG C.
< operation 4: the irradiation ＞ of energy line
Use the surface temperature of temperature sensor measurement silicon substrate, the silicon substrate in confirmation experiment
After surface temperature is identical with setting, to this silicon substrate irradiate xenon lamp (exposure wavelength: 220～
2000nm, exposure intensity: 2.5W/cm2) 2 minutes.
< operation 5: the SEM of silicon substrate observes ＞
By the etch processes compositions on the silicon substrate experiencing above-mentioned operation 4 with by etch processes
After the residue produced removes, observed the table of silicon substrate by sweep electron microscope (SEM)
Face shape.The SEM image of silicon substrate is represented in Figure 19.
As can be clear and definite from Figure 19, it is thus identified that at the Pyramid formed by alkali etching process
The side of texture (main texture), formed as the crystal anisotropy erosion for (111) face
The minute aperture (secondary texture) of the triangular prism shape carved.
Embodiment 25
< operation 1: etch processes ＞ carried out by MEC-75
N-fluoro-3-picoline tetrafluoroborate (MEC-75) is heated to 150 DEG C makes it melt
Solve, coat on silicon substrate.
< operation 2: the temperature of silicon substrate controls ＞
In the heating plate of band refrigerating function, it is placed through the silicon substrate that above-mentioned operation 1 obtains,
After plate temperature is set as 100 DEG C, silicon substrate is placed 40 minutes in darkroom.It addition, use
The surface temperature of temperature sensor measurement silicon substrate, confirm experiment in silicon substrate surface temperature with
Set identical.
< operation 3: the SEM of silicon substrate observes ＞
By experience above-mentioned operation 2 silicon substrate on MEC-75 and by etch processes produce residual
After slag removes, observed the surface configuration of silicon substrate by sweep electron microscope (SEM).
The SEM image of silicon substrate is represented in fig. 20.
< operation 4: the cloth ＞ of etch processes compositions
With 1 12 (molar concentration rate) mixing pyridine and Fluohydric acid., obtain at 125 μ L etchings
Reason compositions, then by this erosion on the silicon substrate that the SEM completing above-mentioned operation 3 observes
Carve composition for treating and be coated into 5mm thickness with the scope that 5mm is square.
< operation 5: the temperature of silicon substrate controls ＞
In the heating plate of band refrigerating function, it is placed through the silicon substrate that above-mentioned operation 4 obtains,
Plate temperature is set as 100 DEG C.
< operation 6: the irradiation ＞ of energy line
Use the surface temperature of temperature sensor measurement silicon substrate, the silicon substrate in confirmation experiment
After surface temperature is identical with setting, to this silicon substrate irradiate xenon lamp (exposure wavelength: 220～
2000nm, exposure intensity: 2.5W/cm2) 4 minutes.
< operation 7: the SEM of silicon substrate observes ＞
By the etch processes compositions on the silicon substrate experiencing above-mentioned operation 6 with by etch processes
After the residue produced removes, observed the table of silicon substrate by sweep electron microscope (SEM)
Face shape.The SEM image of silicon substrate is represented in fig. 20.
As Figure 20 can be clear and definite, it is thus identified that formed in the etch processes by being carried out by MEC-75
The side of texture of inverted pyramid shape, form the elongated ditch of transverse direction.
Claims (11)
1. an etch processes compositions, it is characterised in that:
This etch processes compositions contains nitrogenous aromatic heterocyclic compounds and fluohydric acid gas.
2. etch processes compositions as claimed in claim 1, it is characterised in that:
Nitrogenous aromatic heterocyclic compounds is pyridine or derivatives thereof.
3. etch processes compositions as claimed in claim 2, it is characterised in that:
Pyridine or derivatives thereof is the compound shown in following formula (1),
In formula, adjacent R1And R2、R2And R3、R3And R4Or R4And R5Can connect and
Formation-CR6=CR7-CR8=CR9-, R1、R2、R3、R4、R5、R6、R7、R8、
And R9Represent: hydrogen atom identical or differently；Halogen atom；Nitro；Hydroxyl；Cyano group；Ammonia
Base formoxyl；Can have selected from halogen atom, hydroxyl, the alkoxyl of carbon number 1～5,
The aryloxy group of carbon number 6～10, the acyl group of carbon number 2～5, carbon number 2～5
The carbon number 1～15 of at least one substituent group in the aryl of acyloxy and carbon number 6～10
Alkyl；Can have at least 1 in the aryl of halogen atom and carbon number 6～10
Plant the thiazolinyl of the carbon number 1～15 of substituent group；Can have selected from halogen atom and carbon atom
The alkynyl of the carbon number 1～15 of at least one substituent group in the aryl of several 6～10；Permissible
The carbon with at least one substituent group in the alkyl of halogen atom and carbon number 1～5 is former
The aryl of subnumber 6～15；Can have at least one halogen atom substituent carbon number 1～
The acyl group of 15；Can have in the aryl of halogen atom and carbon number 6～10 at least
The alkoxy carbonyl group of the carbon number 2～15 of a kind of substituent group；Can have selected from halogen atom and carbon
The aryloxy carbonyl of the carbon number 7～15 of at least one substituent group in the alkyl of atomic number 1～5；
Can have at least one substituent group in the aryl of halogen atom and carbon number 6～10
The alkyl sulphonyl of carbon number 1～15；Can have selected from halogen atom and carbon number
The aryl sulfonyl of the carbon number 6～15 of at least one substituent group in the alkyl of 1～5；Can
To have at least one substituent group in the aryl of halogen atom and carbon number 6～10
The alkyl sulphinyl of carbon number 1～15；Can have selected from halogen atom and carbon number
The aryl sulfonyl kia of the carbon number 6～15 of at least one substituent group in the alkyl of 1～5；
Can have at least one substituent group in the aryl of halogen atom and carbon number 6～10
The alkoxyl of carbon number 1～15；Can have selected from halogen atom and carbon number 1～5
Alkyl in the aryloxy group of carbon number 6～15 of at least one substituent group；Can have to
The acyloxy of the carbon number 1～15 of few a kind of halogen atom substituent；Can have at least 1
Plant the acyl sulfenyl of the carbon number 1～15 of halogen atom substituent；Can have selected from halogen former
The carbon number 1～15 of at least one substituent group in the aryl of son and carbon number 6～10
Alkane sulfonyl oxy；Can have in the alkyl of halogen atom and carbon number 1～5 extremely
The aryl-sulfonyl oxygen of the carbon number 6～15 of few a kind of substituent group；Can have selected from carbon former
The amino of at least one substituent group in the alkyl of subnumber 1～5 and the aryl of carbon number 6～10
Formoxyl；Can have at least one in the acyl group and halogen atom of carbon number 1～5
The amino of substituent group；Can have selected from halogen atom, the aryl of carbon number 6～10 and carbon
The N-alkylated pyrazole of the carbon number 6～15 of at least one substituent group in the alkyl of atomic number 1～5
Pyridine alkali；Can have selected from halogen atom, the aryl of carbon number 6～10 and carbon number
The N-aryl pyridinium salt of the carbon number 11～15 of at least one substituent group in the alkyl of 1～5
Base；Or organic polymer chain.
4. the etch processes compositions as according to any one of claims 1 to 3, its feature exists
In: this etch processes compositions is possibly together with oxidant.
5. the etch processes compositions described in claim 4, it is characterised in that:
Oxidant is selected from hydrogen peroxide, peracetic acid and the oxide of nitrogenous aromatic heterocyclic compounds
In at least one.
6. an etching processing method, it is characterised in that:
This etching processing method includes that (1) makes the etching according to any one of Claims 1 to 5
The operation that composition for treating contacts with treated object.
7. etching processing method as claimed in claim 6, it is characterised in that:
This etching processing method also includes the operation of (2-1) heating treated object.
Etching processing method the most as claimed in claims 6 or 7, it is characterised in that:
This etching processing method also includes (2-2) combining with etch processes at treated object
The operation of irradiation energy line on the face of thing contact.
9. the etching processing method as according to any one of claim 6～8, it is characterised in that:
Treated object is semi-conducting material or insulating material.
10. an etch processes thing, it is characterised in that:
This etch processes thing is by the etching processing method according to any one of claim 6～9
Obtain.
11. 1 kinds of solaodes, it is characterised in that:
This solaode comprises the etch processes thing described in claim 10.
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| US11820751B2 (en) | 2021-01-27 | 2023-11-21 | Vandria Sa | Urolithin derivatives and methods of use thereof |
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| CN102498188A (en) * | 2009-09-18 | 2012-06-13 | 默克专利股份有限公司 | Ink jet printable etching inks and associated process |
| CN102569058A (en) * | 2010-12-21 | 2012-07-11 | 东友Fine-Chem股份有限公司 | Corrosion agent composition used for ohmic contact layer |
| CN103733357A (en) * | 2011-08-12 | 2014-04-16 | 国立大学法人大阪大学 | Etching method and method for performing surface processing on solid material for solar cell |
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| CN102498188A (en) * | 2009-09-18 | 2012-06-13 | 默克专利股份有限公司 | Ink jet printable etching inks and associated process |
| CN102569058A (en) * | 2010-12-21 | 2012-07-11 | 东友Fine-Chem股份有限公司 | Corrosion agent composition used for ohmic contact layer |
| CN103733357A (en) * | 2011-08-12 | 2014-04-16 | 国立大学法人大阪大学 | Etching method and method for performing surface processing on solid material for solar cell |
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| KR20190005460A (en) * | 2017-07-06 | 2019-01-16 | 오씨아이 주식회사 | Etching compositions and etching method using the same |
| KR102336865B1 (en) | 2017-07-06 | 2021-12-09 | 오씨아이 주식회사 | Etching compositions and etching method using the same |
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