CN104471715B

CN104471715B - Passivation layer is formed with compositions, the semiconductor substrate of band passivation layer and manufacture method, solar cell device and manufacture method thereof and solaode

Info

Publication number: CN104471715B
Application number: CN201380036883.5A
Authority: CN
Inventors: 足立修郎; 足立修一郎; 吉田诚人; 野尻刚; 仓田靖; 田中彻; 织田明博; 早坂刚
Original assignee: Hitachi Chemical Co Ltd
Current assignee: Showa Denko Materials Co ltd
Priority date: 2012-07-12
Filing date: 2013-07-12
Publication date: 2016-12-07
Anticipated expiration: 2033-07-12
Also published as: TWI615395B; CN106935664A; TW201412761A; JPWO2014010743A1; CN104471715A; WO2014010743A1; KR20150036286A

Abstract

The passivation layer formation compositions of the present invention comprises the organo-aluminum compound shown in following logical formula (I) and at least one the alkoxide compound in titanium alkoxide, zirconium alkoxides and silicon alkoxide.In following logical formula (I), R¹Separately represent the alkyl of carbon number 1～8；N represents the integer of 0～3；X²And X³Separately represent oxygen atom or methylene；R²、R³And R⁴Separately represent hydrogen atom or the alkyl of carbon number 1～8.

Description

Passivation layer formation compositions, the semiconductor substrate of band passivation layer and manufacture method thereof, Solar cell device and manufacture method thereof and solaode

Technical field

The present invention relates to passivation layer formation compositions, the semiconductor substrate of band passivation layer and manufacture method, solar energy Cell device and manufacture method thereof and solaode.

Background technology

The manufacturing process of conventional silicon solar cell element is illustrated.

First, realize high efficiency to promote to fall into photo effect, prepare to be formed with in sensitive surface side the p-type of texture structure Silicon substrate, then, at phosphorous oxychloride (POCl₃), nitrogen, oxygen mixed-gas atmosphere in count at 800 DEG C～900 DEG C The process of ten minutes, is formed uniformly n-type diffusion layer.

In the method that this is conventional, owing to using mixed gas to carry out the diffusion of phosphorus, the most not only on the surface of sensitive surface Form n-type diffusion layer, and also form n-type diffusion layer in side and the back side.Therefore, in order to remove the N-shaped expansion being formed at side Dissipate layer and carry out lateral erosion quarter.Additionally, the n-type diffusion layer being formed at the back side needs to be transformed to p⁺Type diffusion layer.Therefore, at the whole back of the body Topcoating cloth comprises aluminium powder and the Aluminum Paste of binding agent and it is carried out heat treatment (burning till) and forms aluminum electrode, thus makes N-shaped Diffusion layer becomes p⁺Type diffusion layer, obtains Ohmic contact simultaneously.

But, Aluminum Paste the electrical conductivity of the aluminum electrode formed is low.Therefore, in order to reduce film resistor, it is generally formed in The aluminum electrode at the whole back side must have the thickness about 10 μm～20 μm after heat treatment (burning till).And then, due to silicon and aluminum Coefficient of thermal expansion differ widely, therefore, heat treatment (burning till) and cooling during, be formed with in the silicon substrate of aluminum electrode product Raw bigger internal stress, thus cause grain boundary damage (damage), crystal defect to increase and warpage.

In order to solve this problem, it is reduced the coating weight of Aluminum Paste and the method that makes the lower thickness of back electrode layer.But It is if reducing the coating weight of Aluminum Paste, then to become not fill to internal aluminum amount from the diffusion into the surface of p-type silicon semiconductor substrate Point.Result: required BSF (Back Surface Field, back surface field) effect cannot be realized (because of p⁺The existence of type diffusion layer and make Generate the effect that the collection efficiency of carrier improves), therefore produce the problem that the characteristic of solaode reduces.

Based on above-mentioned situation, it is proposed that be formed locally p by giving Aluminum Paste in a part for silicon substrate⁺Type The method (referring for example to No. 3107287 publications of Japanese Patent No.) of the point cantact of diffusion layer and aluminum electrode.

This kind has the solar-electricity of point cantact structure in the side (hereinafter also referred to " rear side ") contrary with sensitive surface In the case of pond, need the recombination velocity at the surface of the part in addition to aluminum electrode suppression minority carrier.As being used for The passivation layer (hereinafter also referred to as " passivation layer ") of the rear side of this purposes, it is proposed that SiO₂Films etc. are (special referring for example to Japan Open 2004-6565 publication).As because forming passivation effect produced by this kind of oxide-film, including by the back gauge of silicon substrate The silicon atom in layer portion uncombined key end-blocking so that cause in conjunction with surface energy level density reduce effect.

Additionally, as suppression minority carrier in conjunction with other method, including the fixed charge utilized in passivation layer The method that produced electric field reduces minority carrier density.Such passivation effect is commonly called field effect, and carries Go out aluminium oxide (Al₂O₃) film etc. is as having the material of negative fixed charge (referring for example to No. 4767110 public affairs of Japanese Patent No. Report).

Such passivation layer is generally by ALD (Atomic Layer Deposition, ald) method or CVD The methods such as (Chemical Vapor Depositon, chemical gaseous phase deposits) method are formed (referring for example to Journal of Applied Physics, 104 (2008), 113703-1～113703-7.).Additionally, as forming oxygen on a semiconductor substrate Change the easy method of aluminum film, it is proposed that utilize sol-gal process method (referring for example to Thin Solid Films, 517 (2009), 6327-6330 and Chinese Physics Letters, 26 (2009), 088102-1～088102-4.).

On the other hand, if form the layer that refractive index is big and passivation effect is the biggest in the sensitive surface side of silicon substrate, then can press down System falls into raising and the recombination velocity of minority carrier of photo effect, and can improve the generating efficiency of solaode.Example The refractive index of film is increased as proposed the oxide-film making the metals such as titanium and aluminum be combined gained by utilizing sol-gal process to be formed Method (referring for example to Japanese Journal of Applied Physics, 45 (2006), 5894～5901.).

Summary of the invention

The problem that invention is to be solved

Journal of Applied Physics, 104 (2008), method described in 113703-1～113703-7. Comprising the complicated manufacturing processes such as evaporation, being difficult to put forward large-duty situation so existing.Additionally, for Thin Solid Films, 517 (2009), 6327～6330. and Chinese Physics Letters, 26 (2009), 088102-1～ In the passivation layer formation compositions of the method described in 088102-4., the unfavorable conditions such as gelation can be produced in time dependent ground, protect Deposit stability to be also difficult to deserve to be called abundant.And then, for by Japanese Journal of Applied Physics, 45 (2006), for the passivation layer that the method described in, 5894～5901. obtains, its refractive index is also difficult to deserve to be called the biggest, deposits In the worry of the photocatalysis being derived from titanium oxide, damage may be given to the sealing resin of solar cell device.

The present invention completes in view of above conventional problem, and it is required that its problem is that offer can be formed with easy method Shape and the biggest passivation layer of refractive index and the passivation layer formation compositions of excellent storage stability.Additionally, the present invention Problem also reside in provide to have and use this passivation layer formation compositions gained, passivation layer that refractive index is the biggest band blunt Change the semiconductor substrate of layer and manufacture method, solar cell device and manufacture method thereof and solaode.

For solving the means of problem

As described below for solving the specific means of above-mentioned problem.

<1>a kind of passivation layer formation compositions, it comprises the organo-aluminum compound shown in following logical formula (I) and selected from alkane At least one alkoxide compound in alcohol titanium, zirconium alkoxides and silicon alkoxide.

[changing 1]

[in logical formula (I), R¹Separately represent the alkyl of carbon number 1～8.N represents the integer of 0～3.X²And X³The most solely On the spot represent oxygen atom or methylene.R²、R³And R⁴Separately represent hydrogen atom or the alkyl of carbon number 1～8.]

<2>according to the passivation layer formation compositions described in<1>, it also comprises alkanol niobium.

<3>according to the passivation layer formation compositions described in<2>, wherein, above-mentioned alkanol niobium is selected from ethanol niobium, isopropanol At least one in niobium, normal propyl alcohol niobium, n-butyl alcohol niobium and phenol niobium.

<4>according to the passivation layer formation compositions according to any one of<1>～<3>, wherein, above-mentioned alkoxide chemical combination Thing includes at least above-mentioned titanium alkoxide, and above-mentioned titanium alkoxide is selected from methanol titanium, titanium ethanolate, isopropyl titanate, normal propyl alcohol titanium, n-butyl alcohol At least one in titanium, tert-butyl alcohol titanium, titanium isobutoxide, diisopropoxy bis-acetylacetonate titanium and four (2-ethyl-1-hexanol) titanium.

<5>according to the passivation layer formation compositions according to any one of<1>～<4>, wherein, above-mentioned alkoxide compound Including at least above-mentioned zirconium alkoxides, above-mentioned zirconium alkoxides is selected from ethanol zirconium, zirconium iso-propoxide, zirconium-n-propylate, zirconium-n-butylate, the tert-butyl alcohol At least one in zirconium, acetylacetone,2,4-pentanedione zirconium, trifluoroacetylacetone (TFA) zirconium and hexafluoroacetylacetone zirconium.

<6>according to the passivation layer formation compositions according to any one of<1>～<5>, wherein, above-mentioned alkoxide compound Including at least above-mentioned silicon alkoxide, above-mentioned silicon alkoxide is the silicon alkoxide shown in following logical formula (II).

(R⁵O)_(4-m)SiR⁶ _m (II)

[in logical formula (II), R⁵And R⁶Separately represent the alkyl of carbon number 1～8.M represents the integer of 0～3.]

<7>according to the passivation layer formation compositions according to any one of<1>～<6>, it also comprises resin.

<8>according to the passivation layer formation compositions according to any one of<1>～<7>, it also comprises following logical formula (III) Shown compound.

[changing 2]

<9>semiconductor substrate of a kind of band passivation layer, it has semiconductor substrate and is arranged on above-mentioned semiconductor substrate Whole or the passivation layer of a part, described passivation layer is the passivation layer formation compositions according to any one of<1>～<8> Heat treatment thing.

<10>manufacture method of the semiconductor substrate of a kind of band passivation layer, comprising: to whole on semiconductor substrate or A part gives the passivation layer formation compositions according to any one of<1>～<8>and forms the operation of composition layer；With to upper State composition layer to carry out heat treatment and form the operation of passivation layer.

<11>a kind of solar cell device, it has: p-type layer and n-layer carry out the semiconductor-based of pn joint Plate；Whole or the passivation layer of a part being arranged on above-mentioned semiconductor substrate, described passivation layer is any one of<1>～<8> The heat treatment thing of described passivation layer formation compositions；Be configured at above-mentioned semiconductor substrate selected from above-mentioned p-type layer and N-shaped Electrode on the layer of more than 1 in Ceng.

<12>manufacture method of a kind of solar cell device, comprising: form having to engage p-type layer and n-layer Pn-junction and have on the layer of more than 1 in above-mentioned p-type layer and above-mentioned n-layer electrode semiconductor substrate, tool There is face at least some of of above-mentioned electrode, give the passivation layer formation compositions according to any one of<1>～<8>and formed The operation of composition layer；The operation of passivation layer is formed with combinations thereof nitride layer is carried out heat treatment.

<13>a kind of solaode, it has the solar cell device described in<11>and is configured at above-mentioned solar-electricity Wiring material on the electrode of pond element.

Invention effect

Required form and the biggest passivation of refractive index can be formed with easy method according to the present invention it is possible to provide Layer and the passivation layer formation compositions of excellent storage stability.Additionally, it is also possible according to the present invention to provide there is use The semiconductor substrate of this passivation layer formation compositions gained, passivation layer that refractive index is the biggest band passivation layer and manufacture thereof Method, solar cell device and manufacture method thereof and solaode.

Accompanying drawing explanation

(a) of Fig. 1～(d) of Fig. 1 are the sun with passivation layer schematically showing an embodiment of the invention The sectional view of one example of the manufacture method of energy cell device.

(a) of Fig. 2～(e) of Fig. 2 are the sun with passivation layer schematically showing an embodiment of the invention The sectional view of another example of the manufacture method of energy cell device.

Fig. 3 is the back electrode type solaode with passivation layer schematically showing an embodiment of the invention The sectional view of element.

Detailed description of the invention

In this manual, independent operation be not only in term " operation ", but also have and cannot clearly be different from other work The situation of sequence, as long as can realize the purpose of this operation in this case, is then also contained in this term.Additionally, use "～" show The numerical range gone out represent containing "～" before and after record numerical value respectively as minima and the scope of maximum.And then, close The content of each composition in compositions, in the case of there is the multiple material being equivalent to each composition in the composition, as long as not having There is special instruction, then each mean the total amount of this many kinds of substance present in compositions.Additionally, term " layer " in this manual In addition to the composition of the shape being formed at whole in time comprising and observe in top plan view, also comprise and see in top plan view The composition of the shape of a part it is formed at when examining.

The passivation layer formation compositions of the present invention comprises the organo-aluminum compound shown in following logical formula (I) and (is also referred to as below Make " specific organo-aluminum compound ") and at least one alkoxide compound in titanium alkoxide, zirconium alkoxides and silicon alkoxide (with The most also referred to as " specific alkoxide compound ").Above-mentioned passivation layer formation compositions can also comprise other as required Point.By making passivation layer formation compositions comprise specific organo-aluminum compound and specific alkoxide compound, it is thus possible to Enough passivation layers the biggest with easy method formation required form and refractive index.Additionally, this passivation layer formation compositions Excellent storage stability.

[changing 3]

In logical formula (I), R¹Separately represent the alkyl of carbon number 1～8.N represents the integer of 0～3.X²And X³The most solely On the spot represent oxygen atom or methylene.R²、R³And R⁴Separately represent hydrogen atom or the alkyl of carbon number 1～8.Here, R¹、 R²、R³、R⁴、X²And X³In either one when existing multiple, the multiple groups represented with same symbol existed can be the most identical Or it is different.

Give on a semiconductor substrate and comprise specific organo-aluminum compound and the passivation layer of specific alkoxide compound Formation compositions and form the composition layer of required form, and it is carried out heat treatment (burning till), thus can be excellent by having Different passivation effect and there is the passivation layer of the biggest refractive index be formed as required form.The method of the present invention is without evaporation Device etc., the method that easy and productivity ratio is high.And then, it is not necessary to the operation that mask process etc. are numerous and diverse can form required form Passivation layer.Additionally, above-mentioned passivation layer formation compositions comprises specific organo-aluminum compound and specific alkoxide chemical combination Thing, therefore time dependent ground suppresses the generation of the unfavorable conditions such as gelation to make excellent storage stability.

In this specification, use the device of WT-2000PVN (Shi Meilebo Co., Ltd. of Japan) etc., utilize microwave reflection The useful life of the minority carrier in the semiconductor substrate being formed with passivation layer is measured by the method for photoconductivity decay measurement, thus may be used To evaluate the passivation effect of semiconductor substrate.

Here, useful life τ can utilize the bulk lifetime (bulk of semiconductor-based intralaminar part like that according to following formula (A) lifetime)τ_bτ surface lifetime with semiconductor substrate surface_sRepresent.Little in the surface energy level density of semiconductor substrate surface In the case of, τ_sElongated, result makes useful life τ elongated.Even if additionally, the defects such as the dangling bonds of semiconductor-based intralaminar part become Few, bulk lifetime τ_bAlso can be elongated, make useful life τ the most elongated.I.e., it is possible to evaluate passivation layer by measuring useful life τ Bulk properties with semiconductor substrates such as the interfacial characteristics of semiconductor substrate and dangling bonds.

1/ τ=1/ τ_b+1/τ_s (A)

It addition, useful life is the longest, represent that the recombination velocity of minority carrier is the slowest.Additionally, by using service life The semiconductor substrate that life is long constitutes solar cell device, so that conversion efficiency improves.

(specific organo-aluminum compound)

It is (following that above-mentioned passivation layer formation compositions comprises at least one organo-aluminum compound shown in above-mentioned logical formula (I) Also referred to as " specific organo-aluminum compound ").Above-mentioned organo-aluminum compound comprises the chemical combination being referred to as aluminium alkoxide, aluminium chelate compound etc. Thing, preferably also has aluminum chelate structure on the basis of aluminium alkoxide structure.Additionally, such as Nippon Seramikkusu Kyokai As Gakujitsu Ronbunshi, 97 (1989) 369-399 are described, heat treatment (burning till) is utilized to make the most organic Aluminium compound becomes aluminium oxide (Al₂O₃)。

Can be by being formed have containing the organo-aluminum compound shown in logical formula (I) for passivation layer formation compositions The reason of the passivation layer of excellent passivation effect, the present inventor etc. considers as follows.

Think: by the passivation layer formation group containing specific organo-aluminum compound and specific alkoxide compound The aluminium oxide that compound carries out heat treatment (burning till) and formed easily becomes amorphous state, therefore easily with semiconductor substrate Near interface forms 4 coordination alumina layers, can have by the bigger negative fixed charge caused by 4 coordination aluminium oxidies.And recognize For: this bigger negative fixed charge produces electric field at the near interface of semiconductor substrate, thus can reduce minority carrier Concentration, result makes the carrier recombination velocity on interface be suppressed, therefore can be formed and have the blunt of excellent passivation effect Change layer.And then be additionally considered that: by also comprising specific alkoxide compound on the basis of organo-aluminum compound, so that institute's shape The refractive index of the passivation layer become becomes big.

Here, the 4 coordination alumina layer states on semiconductor substrate surface as the reason of negative fixed charge are permissible Confirm in the following way: utilize and use sweep type transmission electron microscope (STEM, Scanning Transmission Electron Microscope) ELS electron energy loss spectroscopy method (EELS, Electron Energy Loss Spectroscopy) analysis, investigates combination to the section of semiconductor substrate.4 coordination aluminium oxidies are considered as titanium dioxide Silicon (SiO₂) center become the structure of aluminum by silicon isomorphous substitution (isomorphous substitution), and such as zeolite and clay Negative charge source is formed as like that at the interface of silicon dioxide and aluminium oxide.

It addition, the state of the aluminium oxide formed can be by measuring X-ray diffraction spectrogram (XRD, X-ray Diffraction) confirm.For example, it is possible to do not show specific reflection graphic patterns because of XRD and confirm as impalpable structure. Additionally, the negative fixed charge that aluminium oxide has can pass through CV method (Capacitance Voltage measurement, electric capacity Voltage measurement method) it is evaluated.But, for being formed the heat treatment of the aluminium oxide formed by compositions by the passivation layer of the present invention For nitride layer, the alumina layer that the value of the surface energy level density that it is obtained by CV method is sometimes more than formed by ALD or CVD.But It is to form by the passivation layer of the present invention that the field effect of the passivation layer formed by compositions is big and the concentration fall of minority carrier Low, make τ surface lifetime_sElongated.Therefore, surface energy level density does not the most become problem.

In logical formula (I), R¹Separately represent the alkyl of carbon number 1～8, the preferably alkyl of carbon number 1～4.R¹Shown Alkyl both can be straight-chain, it is also possible to be branched.As R¹Shown alkyl, specifically, can enumerate methyl, second Base, propyl group, isopropyl, butyl, isobutyl group, sec-butyl, the tert-butyl group, hexyl, octyl group, 2-ethylhexyl, 3-ethylhexyl etc..Its In, from the viewpoint of storage stability and passivation effect, R¹Shown alkyl is preferably the unsubstituted alkyl of carbon number 1～8, The more preferably unsubstituted alkyl of carbon number 1～4.

In logical formula (I), n represents the integer of 0～3.From the viewpoint of storage stability, n is preferably the integer of 1～3, more It is preferably 1 or 3.Additionally, X²And X³Separately represent oxygen atom or methylene.From the viewpoint of storage stability, preferably Make X²And X³In at least one party be oxygen atom.

R in logical formula (I)²、R³And R⁴Separately represent hydrogen atom or the alkyl of carbon number 1～8.R²、R³And R⁴Shown in Alkyl both can be straight-chain, it is also possible to be branched.R²、R³And R⁴Shown alkyl both can have substituent group, it is also possible to It is unsubstituted alkyl, the most unsubstituted alkyl.As R²、R³And R⁴Shown alkyl, for the alkyl of carbon number 1～8, excellent Elect the alkyl of carbon number 1～4 as.As R²、R³Or R⁴Shown alkyl, for the alkyl of carbon number 1～8, the preferably alkane of carbon number 1～4 Base.Specifically, can enumerate methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, sec-butyl, the tert-butyl group, hexyl, octyl group, 2-ethylhexyl, 3-ethylhexyl etc..

Wherein, from the viewpoint of storage stability and passivation effect, preferably make the R in logical formula (I)²And R³Independently Ground is hydrogen atom or the unsubstituted alkyl of the unsubstituted alkyl of carbon number 1～8, more preferably hydrogen atom or carbon number 1～4.

Additionally, the R from the viewpoint of storage stability and passivation effect, in logical formula (I)⁴It is preferably hydrogen atom or carbon number The unsubstituted alkyl of the unsubstituted alkyl of 1～8, more preferably hydrogen atom or carbon number 1～4.

From the viewpoint of storage stability, the logical preferably n of organo-aluminum compound shown in formula (I) is 1～3 and R⁴Point Not independently be the compound of the alkyl of hydrogen atom or carbon number 1～4.

From the viewpoint of storage stability and passivation effect, logical organo-aluminum compound shown in formula (I) preferably selects It is 0 and R from n¹Separately for the compound of alkyl and integer that n is 1～3, the R of carbon number 1～4¹It is separately carbon The alkyl of several 1～4, X²And X³In at least one party be oxygen atom, R²And R³It is separately hydrogen atom or the alkane of carbon number 1～4 Base, R⁴Be separately hydrogen atom or carbon number 1～4 alkyl compound at least one.

It is 0 and R that logical organo-aluminum compound shown in formula (I) is more desirably selected from n¹It it is separately carbon number 1～4 The compound of unsubstituted alkyl and integer that n is 1～3, R¹It is separately the unsubstituted alkyl of carbon number 1～4, X² And X³In at least one party be on oxygen atom, above-mentioned oxygen atom combine R²Or R³For the alkyl of carbon number 1～4 and at X²Or X³For The R combined on above-mentioned methylene during methylene²Or R³For hydrogen atom, R⁴For at least one in the compound of hydrogen atom.

As the specific organo-aluminum compound (three aluminium alkoxides) that the n in logical formula (I) is 0, specifically, front three can be enumerated Aluminium alcoholates, three aluminum ethylate .s, aluminum isopropylate, three aluminium secondary butylates, Mono-sec-butoxyaluminium diisopropylate, three tert-butyl alcohol aluminum, three n-butyl alcohol Aluminum etc..

Additionally, as the specific organo-aluminum compound of the integer that shown in logical formula (I), n are 1～3, specifically, can Enumerate oacetic acid aluminum-diisopropoxide, methyl-acetoacetic acid aluminum-diisopropoxide, three (oacetic acid) aluminum, single acetyl third Keto acid two (oacetic acid) aluminum, three (acetopyruvic acid) aluminum etc..

Additionally, the specific organo-aluminum compound of the integer that n is 1～3 in logical formula (I) both can use and prepare Organo-aluminum compound, it is possible to use commercially available product.As commercially available product, include, for example Kawaken Fine Chemicals The trade name of Co., Ltd. i.e. ALCH, ALCH-50F, ALCH-75, ALCH-TR, ALCH-TR-20, Alumichelate M, Alumichelate D, Alumichelate A (W) etc..

Additionally, the specific organo-aluminum compound of the integer that n is 1～3 in logical formula (I) can be by by above-mentioned three alkanols Prepared by the compound mixing of aluminum and the above-mentioned ad hoc structure with 2 carbonyls.In addition it is also possible to use commercially available aluminum sequestration Compound.

When the compound of above-mentioned three aluminium alkoxides and the ad hoc structure with 2 carbonyls is mixed, the alkanol of three aluminium alkoxides The compound of at least some of and ad hoc structure of base occurs displacement to form aluminum chelate structure.Now can exist as required Solvent, in addition it is also possible to carry out the interpolation etc. of heat treated, catalyst.By making at least some of displacement of aluminium alkoxide structure For aluminum chelate structure, so that specific organo-aluminum compound is for the stability raising of hydrolysis and polyreaction, and make blunt The storage stability changing layer formation compositions improves further.Additionally, reactive and alkanol niobium described later, titanium alkoxide, alkanol Zirconium and silicon alkoxide closer to, the most easily generate densification, photocatalysis is little and refractive index is big composite oxides.

As the compound of the above-mentioned ad hoc structure with 2 carbonyls, from the viewpoint of reactivity and storage stability, It is preferably selected from least one in beta-diketone compound, beta-diketonate compound and diester malonate.As above-mentioned, there are 2 carbonyls The compound of the ad hoc structure of base, specifically, can enumerate: acetylacetone,2,4-pentanedione, 3-methyl-2,4-pentanedione, 2,3-pentanedione, 3- Ethyl-2,4-pentanedione, 3-butyl-2,4-pentanedione, 2,2,6,6-tetramethyl-3,5-heptadione, 2,6-dimethyl-3,5-heptan Diketone, 6-methyl-2, the beta-diketone compound such as 4-heptadione；Methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, Isobutyl acetoacetate, butyl-acetoacetate, tert-butyl acetoacetate, acetoacetic acid pentyl ester, isoamyl acetoacetate, acetyl second Acid own ester, acetoacetic acid n-octyl, acetoacetic acid heptyl ester, acetoacetic acid 3-pentyl ester, 2-acetyl group cognac oil, 2-butyl acetyl Ethyl acetate, 4,4-dimethyl-3-oxopentanoic acid methyl ester, 4-methyl-3-oxopentanoic acid methyl ester, 2-ethyl acetoacetic ester, Hexyl ethyl acetoacetate, 4-methyl-3-oxopentanoic, isopropyl acetoacetate, 3-oxo ethyl hexanoate, 3-oxo penta Acetoacetic ester, 3-oxopentanoic, 3-oxo methyl caproate, 2-methyl-acetoacetic ester, 3-oxoheptanoate, 3-oxo Methyl heptanoate, 4, the beta-diketonate compound such as 4-dimethyl-3-oxopentanoic；Dimethyl malenate, diethyl malonate, third Dipropyl malona-te, Diisopropyl malonate, malonic acid di-tert-butyl ester, malonic acid di tert butyl carbonate, malonic acid dihexyl, the tertiary fourth of malonic acid Base ethyl ester, methyl-malonic ester, ethyl malonic acid diethylester, diethyl isopropyl, diethyl butylmalonate, The diester malonates etc. such as s-Butylmalonic acid diethylester, iso-butyl diethyl malonate, 1-methyl butyl diethyl malonate.

In the case of above-mentioned specific organo-aluminum compound has aluminum chelate structure, as long as the number of aluminum chelate structure is 1～3, then there is no particular restriction.Wherein, from the viewpoint of storage stability, the number of aluminum chelate structure is preferably 1 or 3, from From the viewpoint of dissolubility, the number of aluminum chelate structure is more preferably 1.The number of aluminum chelate structure such as can be by suitably adjusting Whole above-mentioned three aluminium alkoxides and the blending ratio of compound of chelate can be formed with aluminum and be controlled.In addition it is also possible to from Commercially available aluminum chelate compound suitably selects the compound with desired structure.

In the organo-aluminum compound shown in logical formula (I), from passivation effect and with the mixing of the solvent being added as needed on From the viewpoint of property, specifically, it is preferably used in oacetic acid aluminum-diisopropoxide and aluminum isopropylate at least One, more preferably uses oacetic acid aluminum-diisopropoxide.

The existence of the aluminum chelate structure in above-mentioned specific organo-aluminum compound can utilize commonly used analysis side Method confirms.Infrared spectroscopy spectrum, NMR (Nuclear Magnetic Resonance) spectrum, fusing point etc. such as can be used to confirm.

The containing ratio of the above-mentioned specific organo-aluminum compound comprised in above-mentioned passivation layer formation compositions can basis Needs suitably select.From the viewpoint of storage stability and passivation effect, the containing ratio of organo-aluminum compound is in passivation Layer formation compositions can be set to 1 mass %～70 mass %, preferably 3 mass %～60 mass %, more preferably 5 matter Amount %～50 mass %, more preferably 10 mass %～30 mass %.

Organo-aluminum compound both can be aqueous, it is also possible to for solid, there is no particular restriction.Steady from passivation effect and preservation From the viewpoint of qualitative, when being preferably used in the stability under room temperature (25 DEG C) and use solvent to the dissolubility of solvent or point Dissipate the specific organo-aluminum compound that property is good.By using such specific organo-aluminum compound, thus exist and make institute's shape The homogeneity of the passivation layer become improves, can stably obtain the tendency of required passivation effect further.

(specific alkoxide compound)

The passivation layer formation compositions of the present invention on the basis of specific organo-aluminum compound possibly together with selected from alkanol At least one alkoxide compound (the most also referred to as " specific alkoxide compound ") in titanium, zirconium alkoxides and silicon alkoxide.Pass through Containing at least one compound in specific alkoxide compound such that it is able to generate refraction together with organo-aluminum compound The composite oxides that rate is big, and also can further improve passivation effect.

Compared with the passivation layer only formed by organo-aluminum compound, by the passivation layer formation compositions of the present invention is entered Row heat treatment (burning till) and the refractive index of passivation layer that formed becomes big.Such as being formed with big blunt of refractive index on sensitive surface For changing the solar cell device of layer, owing to the utilization ratio of light improves further, therefore generating efficiency improves.By passivation layer The refractive index of passivation layer that formation compositions is formed is preferably more than 1.4, and more preferably more than 1.6, more preferably 1.6 ～2.5.

As titanium alkoxide, there is no particular restriction, can suitably select to use from commonly used titanium alkoxide.Wherein, From the viewpoint of the resin that the passivation layer being difficult to make with formed contacts etc. decomposes, titanium alkoxide preferably with logical formula (I) institute Show organo-aluminum compound reaction and Composite and form the titanium alkoxide of finer and close composite oxides.As titanium alkoxide, specifically For, methanol titanium, titanium ethanolate, isopropyl titanate, normal propyl alcohol titanium, n-butyl titanium, tert-butyl alcohol titanium, titanium isobutoxide, diisopropyl can be enumerated Epoxide bis-acetylacetonate titanium, four (2-ethyl-1-hexanol) titanium etc..Commonly known titanium alkoxide is carried out obtained by heat treatment (burning till) The refractive index of titanium oxide is bigger.But, titanium oxide itself is being added to situation about using in passivation layer formation compositions Under, the photocatalysis that may be had due to titanium oxide and cause resin contacted with passivation layer etc. lower point of sunlight etc. Solve.On the other hand, in the case of titanium alkoxide is applied to passivation layer formation compositions, titanium alkoxide and organo-aluminum compound one Rise and form composite oxides, photocatalysis can be suppressed, and the passivation layer that refractive index is big can be formed.

As zirconium alkoxides, as long as react with the organo-aluminum compound shown in logical formula (I) and form the alkane of composite oxides Alcohol zirconium, then there is no particular restriction.As zirconium alkoxides, specifically, ethanol zirconium, zirconium iso-propoxide, zirconium-n-propylate, n-butyl alcohol can be enumerated Zirconium, zirconium tert-butoxide, acetylacetone,2,4-pentanedione zirconium, trifluoroacetylacetone (TFA) zirconium, hexafluoroacetylacetone zirconium etc..Commonly known zirconium alkoxides is carried out heat Process zirconic refractive index obtained by (burning till) bigger.But, zirconium oxide itself is being added to passivation layer formation combination In the case of thing uses, the photocatalysis that may be had due to zirconium oxide and cause the resin contacted with passivation layer Decompose down Deng at sunlight etc..On the other hand, in the case of zirconium alkoxides is applied to passivation layer formation compositions, zirconium alkoxides Form composite oxides together with organo-aluminum compound, can suppress photocatalysis, and big blunt of refractive index can be formed Change layer.

Silicon alkoxide is illustrated.By to the passivation layer formation group containing the organo-aluminum compound shown in logical formula (I) The aluminium oxide that compound carries out heat treatment (burning till) and formed easily becomes amorphous state, and partly generates 4 coordination aluminium oxidies. If generating 4 coordination aluminium oxidies, then obtain negative fixed charge.If here, passivation layer formation compositions comprises silicon alkoxide, then leading to Overheating Treatment (burning till) can generate 4 coordination silicon oxides simultaneously.Known 4 coordination silicon oxides can by isomorphous substitution make central atom from Silicon is replaced as aluminum.Therefore, when alumina layer is formed 4 coordination silicon oxide, correspondingly can easily generate and there is negative fixed charge 4 coordination aluminium oxidies.Silicon alkoxide is carried out heat treatment (burning till) although obtained by the refractive index of silicon oxide itself compare aluminium oxide Little, but owing to easily being generated the 4 coordination aluminium oxidies as negative fixed charge source by Composite, therefore so that refraction will not be made The degree that rate declines to a great extent uses silicon alkoxide, thus obtains more excellent passivation effect.

As silicon alkoxide, as long as with the organo-aluminum compound shown in logical formula (I), titanium alkoxide, zirconium alkoxides or as required Contained alkanol niobium reacts and forms the silicon alkoxide of composite oxides, then there is no particular restriction.Wherein, silicon alkoxide is the most following Logical compound shown in formula (II).

(R⁵O)_(4-m)SiR⁶ _m (II)

In formula (II), R⁵And R⁶Separately represent the alkyl of carbon number 1～8.N represents the integer of 0～3.Here, R⁵And R⁶In either one when existing multiple, the multiple R existed⁵Or R⁶Can be the most identical or different.

As silicon alkoxide, specifically, four methanol silicon, tetraethoxide silicon, four propanol silicon etc. can be enumerated.

In the alkoxide compound in titanium alkoxide, zirconium alkoxides and silicon alkoxide, from the reaction with organo-aluminum compound From the viewpoint of property, the refractive index of the composite oxides generated and passivation effect, it is preferably used selected from titanium alkoxide and zirconium alkoxides In at least one, more preferably use at least one in isopropyl titanate, ethanol zirconium and zirconium iso-propoxide, further preferably make By at least one in isopropyl titanate and ethanol zirconium.

Specific alkoxide compound in passivation layer formation compositions, in titanium alkoxide, zirconium alkoxides and silicon alkoxide The total amount of containing ratio be preferably 0.5 mass %～65 mass %, more preferably 1 mass %～65 mass %, further preferably It is 2 mass %～60 mass %.

Additionally, from the viewpoint of the refractive index and passivation effect of the composite oxides generated, above-mentioned specific alkoxide The content of compound is relative to the ratio of the content of the organo-aluminum compound shown in logical formula (I) (specific alkoxide compound/formula (I) organo-aluminum compound shown in) be preferably 0.01～1000, more preferably 0.05～500, more preferably 0.1～ 100。

(alkanol niobium)

Passivation layer formation compositions can contain at least one alkanol niobium.Known alkanol niobium is carried out heat treatment (burning till) Obtained by the refractive index of niobium oxide relatively big, therefore by the passivation layer formation compositions also comprising alkanol niobium is carried out heat treatment (burning till), can obtain the passivation layer that refractive index is bigger.

As alkanol niobium, as long as react with the organo-aluminum compound shown in logical formula (I) and form the alkane of composite oxides Alcohol niobium, then there is no particular restriction.As alkanol niobium, specifically, ethanol niobium, isopropanol niobium, normal propyl alcohol niobium, n-butyl alcohol can be enumerated Niobium, phenol niobium etc..

In the case of passivation layer formation compositions contains alkanol niobium, the containing ratio of alkanol niobium is in passivation layer formation group In the gross mass of compound be preferably 0.2 mass %～50 mass %, more preferably 0.5 mass %～48 mass %, the most excellent Elect 1 mass %～46 mass % as.

Additionally, in the case of passivation layer formation compositions contains alkanol niobium, from the folding of the composite oxides generated From the viewpoint of penetrating rate and passivation effect, the content of alkanol niobium relative to the organo-aluminum compound shown in logical formula (I) content it Be preferably 0.01～1000 than (organo-aluminum compound shown in alkanol niobium/logical formula (I)), more preferably 0.05～500, further It is preferably 0.1～100.

And then, in the case of passivation layer formation compositions contains alkanol niobium, from the folding of the composite oxides generated From the viewpoint of penetrating rate and passivation effect, the total content of specific alkoxide compound and alkanol niobium is relative to shown in logical formula (I) The ratio of the content of organo-aluminum compound is preferably 0.01～1000, more preferably 0.05～500, more preferably 0.1～ 100。

In passivation layer formation compositions, logical organo-aluminum compound shown in formula (I), specific alkoxide compound and root In the gross mass of passivation layer formation compositions, 1 mass %～70 matter it are preferably according to total containing ratio of the alkanol niobium contained by needs Amount %, more preferably 3 mass %～60 mass %, more preferably 5 mass %～50 mass %.

(resin)

Passivation layer formation compositions can also comprise at least one resin.By comprising resin, so that at quasiconductor The shape stability of the composition layer giving above-mentioned passivation layer formation compositions on substrate and formed improves further, Ke Yi The region being formed with combinations thereof nitride layer is formed selectively passivation layer according to required form.

There is no particular restriction for the kind of resin.Resin is preferably and gives passivation layer formation compositions on a semiconductor substrate Time viscosity can be adjusted to be formed the resin of the scope of good pattern.As resin, specifically, can enumerate: polyethylene Alcohol；Polyacrylamide；Polyvinyl lactam class；Polyvinyl pyrrolidone；Poly(ethylene oxide) class；Polysulfonate acid；Polyacrylamide Alkyl sulfonic acid；Cellulose；The celluloses such as the cellulose ether of carboxymethyl cellulose, hydroxyethyl cellulose, ethyl cellulose etc. derive Thing；Gelatin and gelatine derivative；Starch and starch derivatives；Sodium alginate and sodium alginate derivant；Xanthan gum and xanthan gum Derivant；Guar gum and guar derivative；Scleroglucan and scleroglucan derivant；Tragacanth and Tragacanth derivant；Stick with paste Essence and dextrin derivative；(methyl) acrylic resin；(methyl) acrylate (such as (methyl) alkyl acrylate tree Fat, (methyl) dimethylaminoethyl acrylate resin etc.)；Butadiene resin, styrene resin, silicone resin, these materials Copolymer etc..These resins can be used alone a kind or are applied in combination two or more.

In these resins, from the viewpoint of storage stability and patternability, be preferably used do not have acidity and The resinene of the functional group of alkalescence, even if from the viewpoint of also being able to can easily be accommodated viscosity and thixotropy when content is few, More preferably use cellulose derivative.

Additionally, the molecular weight of these resins there is no particular restriction, preferably in view of viscous needed for passivation layer formation compositions Degree suitably adjusts.From the viewpoint of storage stability and patternability, the weight average molecular weight of above-mentioned resin is preferably 1,000～10,000,000, more preferably 3,000～5,000,000.It addition, the weight average molecular weight of resin is by using standard The standard curve of polystyrene is converted by the molecular weight distribution using GPC (gel permeation chromatography) to record and obtains.

In the case of passivation layer formation compositions contains resin, containing in the passivation layer formation compositions of resin Rate can the most suitably select.Such as in the gross mass of passivation layer formation compositions, the containing ratio of resin is excellent Elect 0.1 mass %～30 mass % as.From the viewpoint of showing the thixotropy being more readily formed pattern, above-mentioned containing ratio is more It is preferably 1 mass %～25 mass %, more preferably 1.5 mass %～20 mass %, the most preferably 1.5 matter Amount %～10 mass %.

In the case of passivation layer formation compositions contains resin, above-mentioned in above-mentioned passivation layer formation compositions has Machine aluminium compound can the most suitably select containing ratio with above-mentioned resin.Wherein, from patternability and guarantor From the viewpoint of depositing stability, resin-phase preferably setting containing ratio (resin/organo-aluminum compound) for organo-aluminum compound It is 0.001～1000, more preferably 0.01～100, more preferably 0.1～1.

(higher boiling point materials)

Passivation layer formation compositions can be used together higher boiling point materials with resin or use higher boiling point materials The instead material of resin.Higher boiling point materials is preferably and easily gasifies and without carrying out the chemical combination of ungrease treatment when heating Thing.Additionally, higher boiling point materials particularly preferably can maintain the full-bodied higher boiling point materials of printing shape after printing coating. As meeting the material of these conditions, include, for example the isobornyl cyclohexanol shown in logical formula (III).

[changing 4]

This isobornyl cyclohexanol shown in logical formula (III) is " the Terusolve MTPH " being commercially obtained in that (NIPPON TERPENE CHEMICALS, INC., trade name).The boils up till of isobornyl cyclohexanol 308 DEG C～318 DEG C, And need not carry out when removing this isobornyl cyclohexanol from composition layer using the de-of heat treatment (burning till) as resin Fat processes, and is vaporized by heating and it just can be made to disappear.Therefore, passivation layer formation compositions is being coated semiconductor-based In drying process after on plate, solvent contained as required in compositions and the big portion of isobornyl cyclohexanol can be removed Point, and the black residue after heat treatment (burning till) can be suppressed.

In the case of passivation layer formation compositions contains higher boiling point materials, the containing ratio of higher boiling point materials is at passivation layer The gross mass of formation compositions is preferably 0.5 mass %～85 mass %, more preferably 1 mass %～80 mass %, spy You Xuanwei 2 mass %～80 mass %.

(solvent)

Above-mentioned passivation layer formation compositions can contain solvent.By making passivation layer formation compositions contain solvent, Thus exist and be easier to adjust viscosity, make imparting improve further and the tendency of passivation layer evenly can be formed.Make For above-mentioned solvent, there is no particular restriction, can the most suitably select.Wherein, it is preferably able to by dissolving logical formula (I) Shown organo-aluminum compound and specific alkoxide compound and form the solvent of homogeneous solution, more preferably containing at least one has Machine solvent.

As solvent, specifically, can enumerate: acetone, butanone, methyl n-pro-pyl ketone, methyl isopropyl Ketone, methyl Normal-butyl ketone, methyl iso-butyl ketone (MIBK), methyl-n-amyl ketone, methyl n hexyl ketone, metacetone, dipropyl ketone, diisobutyl ketone, Trimethyl nonanone, Ketohexamethylene, Ketocyclopentane, methyl cyclohexanone, 2, the ketone series solvent such as 4-pentanedione, acetonyl acetone；Anaesthetie Ether, Methyl ethyl ether, methyl n-propyl ether, Di Iso Propyl Ether, oxolane, methyltetrahydrofuran, dioxane, dimethyldialkylammonium, Ethylene glycol dimethyl ether, ethylene glycol bisthioglycolate ethylether, ethylene glycol bisthioglycolate n-propyl ether, ethylene glycol bisthioglycolate butyl ether, diethylene glycol dimethyl Ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl n-propyl ether, the positive fourth of diethylene glycol methyl Base ether, diethylene glycol diη-propyl ether, diethylene glycol di-n-butyl ether, diethylene glycol diola, triethylene glycol diformazan Base ether, triethylene glycol Anaesthetie Ether, triethylene glycol methyl ethyl ether, triethylene glycol methyl n-butyl ether, the positive fourth of triethylene glycol two Base ether, triethylene glycol diola, TEG dimethyl ether, TEG Anaesthetie Ether, TEG Methylethyl Ether, TEG methyl n-butyl ether, TEG di-n-butyl ether, TEG diola, TEG two are just Butyl ether, propylene glycol dimethyl ether, propylene glycol Anaesthetie Ether, propylene glycol diη-propyl ether, propylene glycol dibutyl ethers, dipropylene glycol Dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ethylether, dipropylene glycol methyl n-butyl ether, dipropylene glycol two N-propyl ether, dipropylene glycol di-n-butyl ether, dipropylene glycol methyl n-hexyl ether, tripropylene glycol dimethyl, tripropylene glycol two Ethylether, tripropylene glycol methyl ethyl ether, tripropylene glycol methyl n-butyl ether, tripropylene glycol di-n-butyl ether, tripropylene glycol first Base n-hexyl ether, four propylene glycol dimethyl ether, four propylene glycol Anaesthetie Ethers, four propylene glycol methyl ethyl ethers, four propylene glycol methyl The ether systems such as n-butyl ether, four propylene glycol di-n-butyl ethers, four propylene glycol methyl n-hexyl ethers, four propylene glycol di-n-butyl ethers are molten Agent；Methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, N-amyl acetate, sec-amyl acetate, acetic acid 3-methoxybutyl, methyl amyl acetate, acetic acid 2-ethyl butyl ester, acetic acid 2-ethyl Own ester, acetic acid 2-(2-Butoxyethoxy) ethyl ester, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, nonyl acetate, Methyl acetoacetate, ethyl acetoacetate, acetic acid diethylene ester, acetic acid TC ester, acetic acid two Propylene glycol methyl ether-ether, acetic acid dipropylene glycol ethyl ether ester, diacetate glycol ester, acetic acid methoxy triethylene ester, propanoic acid Ethyl ester, n-butyl propionate, propanoic acid isopentyl, ethyl oxalate, dibutyl oxalate, methyl lactate, ethyl lactate, the positive fourth of lactic acid Ester, N_amyl lactate, Ethylene glycol methyl ether propionic ester, glycol ethyl ether propionic ester, Ethylene glycol methyl ether acetas, ethylene glycol Monoethyl ether acetate, methyl proxitol acetate, propylene glycol ethyl ether acetas, propylene glycol propyl ether acetas, γ-Ding Nei The ester series solvent such as ester, gamma-valerolactone；Acetonitrile, N-Methyl pyrrolidone, N-ethyl pyrrolidone, N-propyl pyrrole alkanone, N- Butyl pyrrolidine ketone, N-hexyl ketopyrrolidine, N-cyclohexyl pyrrolidone, DMF, N, N-dimethylacetamide The aprotic polar solvent such as amine, dimethyl sulfoxide；Dichloromethane, chloroform, dichloroethanes, benzene,toluene,xylene, hexane, pungent The hydrophobic organic solvents such as alkane, ethylo benzene, 2 ethyl hexanoic acid, methyl iso-butyl ketone (MIBK), butanone；Methanol, ethanol, normal propyl alcohol, different Propanol, n-butyl alcohol, isobutanol, sec-butyl alcohol, the tert-butyl alcohol, n-amyl alcohol, isoamyl alcohol, 2-methyl butanol, sec-amyl alcohol, tert-pentyl alcohol, 3-first Epoxide butanol, hexanol, 2-methyl anyl alcohol, secondary hexyl alcohol, 2-ethyl butanol, secondary enanthol, n-octyl alcohol, 2-Ethylhexyl Alcohol, sec-octyl alcohol, N-nonyl alcohol, Decanol, secondary tip-nip, Exxal 12, secondary tetradecanol, secondary heptadecanol, Hexalin, methyl cyclohexanol, The alcohol systems such as benzylalcohol, ethylene glycol, 1,2-PD, 1,3 butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol are molten Agent；Ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol list phenyl ether, diethylene glycol monomethyl ether, diethylene glycol list second Base ether, diethylene glycol list n-butyl ether, diethylene glycol list n-hexyl ether, ethoxytriglycol, TEG list n-butyl ether, The glycol monoethers systems such as propylene glycol monomethyl ether, DPGME, dihydroxypropane single-ethyl ether, tripropylene glycol monomethyl ether Solvent；α-terpinene, α-terpinol, myrcene, alloocimene, limonene, cinene,_α-pinene, nopinene, terpineol (terpineol), the terpene series solvent such as carvone, ocimene, phellandrene；Water etc..These solvents can be used alone a kind or combination Use two or more.

Wherein, from the viewpoint of to the imparting of semiconductor substrate and patternability, above-mentioned solvent preferably comprises choosing At least one in terpene series solvent, ester series solvent and alcohol series solvent, more preferably comprises at least one in terpene series solvent.

In the case of passivation layer formation compositions comprises solvent, the containing ratio of solvent considers that imparting property, pattern are formed Property and storage stability determine.Such as, from the viewpoint of the imparting and patternability of compositions, the containing ratio of solvent 5 mass %～98 mass %, more preferably 10 mass %～95 mass % it are preferably in passivation layer formation compositions.

(other additive)

Above-mentioned passivation layer formation compositions can contain acid compound or alkali compounds.In passivation layer formation group In the case of compound contains acid compound or alkali compounds, from the viewpoint of storage stability, preferably make acid chemical combination The containing ratio of thing or alkali compounds is respectively below 1 mass %, more preferably 0.1 matter in passivation layer formation compositions Amount below %.

As acid compound, Bronsted acid (bronsted acid) and lewis acid can be enumerated.Specifically, Can enumerate: the mineral acid such as hydrochloric acid, nitric acid；The organic acid etc. such as acetic acid.Additionally, as alkali compounds, cloth Lanace platform can be enumerated Moral alkali and lewis base.Specifically, can enumerate: the inorganic base such as alkali metal hydroxide, alkaline earth metal hydroxide；Trialkyl The organic base such as amine, pyridine etc..

(physics value)

There is no particular restriction for the viscosity of above-mentioned passivation layer formation compositions, can be according to the imparting side to semiconductor substrate Methods etc. suitably select.The such as viscosity of passivation layer formation compositions can be set to 0.01Pa s～10000Pa s.Its In, from the viewpoint of patternability, the viscosity of passivation layer formation compositions is preferably 0.1Pa s～1000Pa s. It addition, above-mentioned viscosity uses rotary shear viscosity meter with shear rate 1.0s at 25 DEG C^-1It is measured.

Additionally, the shear viscosity of passivation layer formation compositions there is no particular restriction, preferably make passivation layer formation combine Thing has thixotropy.Especially in the case of passivation layer formation compositions comprises resin, from the viewpoint of patternability, Shear rate 1.0s^-1Time shear viscosity η₁Divided by shear rate 10s^-1Time shear viscosity η₂And the thixotropic ratio (η calculated₁/η₂) It is preferably 1.05～100, more preferably 1.1～50.It addition, shear viscosity uses is provided with cone-plate (diameter 50mm, cone angle 1 °) Rotary shear viscosity meter be measured at temperature 25 DEG C.

On the other hand, higher boiling point materials is contained in the case of replacing resin in passivation layer formation compositions, from pattern From the viewpoint of formative, shear rate 1.0s^-1Time shear viscosity η₁Divided by shear rate 1000s^-1Time shear viscosity η₃ And the thixotropic ratio (η calculated₁/η₃) it is preferably 1.05～100, more preferably 1.1～50.

(manufacture method of passivation layer formation compositions)

For the manufacture method of above-mentioned passivation layer formation compositions, there is no particular restriction.For example, it is possible to be beneficial to generally make Mixed method by the organo-aluminum compound shown in logical formula (I), specific alkoxide compound and resin contained as required, Solvent etc. mix, thus manufacture above-mentioned passivation layer formation compositions.Further, it is also possible to by after resin is dissolved in solvent It is mixed with the organo-aluminum compound shown in logical formula (I) and specific alkoxide compound and manufactures above-mentioned passivation layer formation group Compound.

And then, it is also possible to by aluminium alkoxide, the compound that can form chelate with aluminum are mixed and prepare logical formula (I) institute The organo-aluminum compound shown.At this point it is possible to use solvent as required, it is also possible to carry out heat treated.Can also be by by this Organo-aluminum compound shown in logical formula (I) prepared by sample and specific alkoxide compound and resin or wrap resiniferous solution and mix Manufacture passivation layer formation compositions.

It addition, the content of composition contained in above-mentioned passivation layer formation compositions and each composition can use differential heat- Thermogravimetric amount measures spectrum analysis, the high-efficient liquids such as heat analysis, nuclear magnetic resonance, NMR (NMR), infrared spectrometry (IR) such as (TG/DTA) simultaneously Phase chromatograph (HPLC), gel permeation chromatography (GPC) isochromatic spectrum analysis etc. confirm.

The semiconductor substrate of the band passivation layer of the present invention, it has semiconductor substrate and is arranged on above-mentioned semiconductor substrate Whole or the passivation layer of a part, described passivation layer is that the heat treatment thing of the passivation layer formation compositions of the present invention (burns till Thing).The semiconductor substrate of above-mentioned band passivation layer is by having the heat treatment nitride layer (burned material of above-mentioned passivation layer formation compositions Layer) i.e. passivation layer and demonstrate excellent passivation effect.

There is no particular restriction for semiconductor substrate, can carry out suitably according to purpose from commonly used semiconductor substrate Select.As semiconductor substrate, can be set forth in doping (diffusion) in silicon, germanium etc. has the semiconductor-based of n-type impurity or p-type impurity Plate.Wherein, preferably silicon substrate.Additionally, semiconductor substrate both can be p-type semiconductor substrate, it is also possible to be n-type semiconductor base Plate.Wherein, from the viewpoint of passivation effect, the face preferably forming passivation layer is the semiconductor substrate of p-type layer.Above-mentioned partly lead P-type layer on structure base board both can be derived from the p-type layer of p-type semiconductor substrate, it is also possible to is with p-diffusion layer or p⁺Type expands The form dissipating layer is formed at the p-type layer on n-type semiconductor substrate or p-type semiconductor substrate.

Additionally, the thickness of above-mentioned semiconductor substrate there is no particular restriction, suitably can select according to purpose.Such as, The thickness of semiconductor substrate can be set to 50 μm～1000 μm, preferably 75 μm～750 μm.

There is no particular restriction for the average thickness of the passivation layer being formed on above-mentioned semiconductor substrate, can carry out according to purpose Suitably select.Such as, the average thickness of passivation layer is preferably 5nm～50 μm, more preferably 10nm～30 μm, more preferably 15nm～20 μm.The average thickness of passivation layer can utilize interference formula film thickness gauge etc. to measure.

The semiconductor substrate of above-mentioned band passivation layer can apply to solar cell device, light-emitting diode etc..Example As, by being applied to solar cell device, it is hereby achieved that the solar cell device that conversion efficiency is excellent.By above-mentioned In the case of semiconductor substrate with passivation layer is applied to solar cell device, passivation layer is preferably provided at solaode unit The sensitive surface side of part.

The manufacture method of the semiconductor substrate of the band passivation layer of the present invention, comprising: to whole on semiconductor substrate or A part gives the passivation layer formation compositions of the present invention and forms the operation of composition layer；Carry out with to combinations thereof nitride layer Heat treatment (burning till) and form the operation of passivation layer.Above-mentioned manufacture method can also contain other operation the most further.

By using above-mentioned passivation layer formation compositions, required form can be formed with easy method and there is excellence Passivation effect and the passivation layer of bigger refractive index.

The manufacture method of the semiconductor substrate of above-mentioned band passivation layer was preferably gone back before forming the operation of combinations thereof nitride layer There is the operation giving aqueous alkali on a semiconductor substrate.I.e., preferably above-mentioned passivation layer formation compositions is being imparted to With the surface of aqueous alkali washing semi-conductor substrate before on semiconductor substrate.By washing with aqueous alkali, can remove Go to be present in the Organic substance of semiconductor substrate surface, microgranule etc., and make passivation effect improve further.Molten as utilizing aqueous alkali The washing methods of liquid, can illustrate commonly known RCA washing etc..Such as, semiconductor substrate be impregnated in ammonia-hydrogen peroxide In the mixed solution of water, and process at 60 DEG C～80 DEG C, thus can remove Organic substance and microgranule and wash.Wash The time of washing is preferably 10 seconds～10 minutes, more preferably 30 seconds～5 minutes.

In RCA washs, first, semiconductor substrate is put in diluted hydrofluoric acid aqueous solution (HF), make the relatively thin of surface Si oxide-film dissolves, and will be attached to multiple foreign body thereon and remove the most simultaneously.And then, utilize ammonia as described above (NH₄OH)-hydrogen peroxide (H₂O₂) mixed solution remove Organic substance and microgranule, then, utilize hydrochloric acid (HC1) and hydrogen peroxide (H₂O₂) remove metal class.Then, ultra-pure water is utilized to complete last washing.

Give above-mentioned passivation layer formation compositions on a semiconductor substrate and form the method for composition layer and there is no especially Limit.Such as, the known coating process of use etc. can be enumerated and give above-mentioned passivation layer formation compositions on a semiconductor substrate Method.Specifically, infusion process, print process, spin-coating method, spread coating, nebulization, scraper plate method, rolling method, ink-jet method can be enumerated Deng.Wherein, from the viewpoint of patternability, the most various print processes, ink-jet method etc..

The imparting amount of above-mentioned passivation layer formation compositions suitably can select according to purpose.For example, it is possible to according to The thickness making formed passivation layer becomes the mode of aftermentioned desired thickness and suitably adjusts the imparting of passivation layer formation compositions Amount.

To by passivation layer formed the composition layer formed by compositions carry out heat treatment (burning till) and formed derive from above-mentioned The heat treatment nitride layer (burning till nitride layer) of composition layer, such that it is able to form passivation layer on a semiconductor substrate.

About heat treatment (burning till) condition of composition layer, as long as can be by shown in logical formula (I) contained in composition layer Organo-aluminum compound and specific alkoxide compound be converted into the aluminium oxide (Al as its heat treatment thing (burned material)₂O₃) and Composite oxides, then be not particularly limited.Wherein, it is preferably able to be formed comprise and not there is specific crystalline texture and amorphous Al₂O₃Heat treatment (burning till) condition of layer.By making passivation layer by the Al comprising amorphous₂O₃Layer constitute, can more have Make passivation layer electronegative to effect, and more excellent passivation effect can be obtained.Specifically, heat treatment (burning till) temperature is excellent Elect 400 DEG C～900 DEG C as, more preferably 450 DEG C～800 DEG C.Additionally, heat treatment (burning till) time can according to heat treatment (burn Becoming) temperature etc. suitably selects.Such as can be set to 0.1 hour～10 hours, preferably 0.2 hour～5 hours.

There is no particular restriction to utilize the thickness of passivation layer that the manufacture method of the semiconductor substrate of above-mentioned band passivation layer manufactures, Suitably can select according to purpose.The average thickness of such as passivation layer is preferably 5nm～50 μm, more preferably 10nm～30 μm, more preferably 15nm～20 μm.

It addition, the average thickness of the passivation layer formed is by using contact pin type difference in height-surface-profile measuring instrument (example Such as Ambios company), interfere the thickness of formula film thickness gauge (such as FILMETRICS company) etc. conventionally mensuration 3, Calculate its arithmetic mean of instantaneous value again.

The manufacture method of the semiconductor substrate of above-mentioned band passivation layer can giving after passivation layer formation compositions and Heat treatment (burning till) is utilized also to have being formed the compositions formed by compositions by passivation layer before forming the operation of passivation layer The withering operation of layer.By having operation withering to composition layer, can be formed and have evenly The passivation layer of passivation effect.

As long as operation withering to composition layer can will be possibly comprised in passivation layer formation compositions At least some of removing of solvent, then there is no particular restriction.Dried such as can be set to carry out at 30 DEG C～250 DEG C 1 minute～the heat treated of 60 minutes, be preferably and carry out 3 minutes～the heat treated of 40 minutes at 40 DEG C～220 DEG C.This Outward, dried both can be carried out at ambient pressure, it is also possible under reduced pressure carries out.

In the case of passivation layer formation compositions comprises resin, the manufacturer of the semiconductor substrate of above-mentioned band passivation layer Method giving after passivation layer formation compositions and can utilize heat treatment (burning till) also to have before forming the operation of passivation layer The operation of ungrease treatment is carried out to being formed, by passivation layer, the composition layer formed by compositions.Owing to having, composition layer is carried out The operation of ungrease treatment, therefore can form the passivation layer with semiconductor substrate passivation effect evenly.

As long as the operation that composition layer carries out ungrease treatment can will be possibly comprised in passivation layer formation compositions At least some of removing of resin, then there is no particular restriction.Ungrease treatment such as can be set to enter at 250 DEG C～400 DEG C Row 3 minutes～the heat treated of 120 minutes, be preferably at the heating carrying out 10 minutes～60 minutes at 300 DEG C～450 DEG C Reason.Additionally, ungrease treatment is carried out the most in the presence of oxygen, carry out the most in an atmosphere.

The solar cell device of the present invention, it has: p-type layer and n-layer carry out the semiconductor-based of pn joint Plate；Whole or the passivation layer of a part being arranged on above-mentioned semiconductor substrate, described passivation layer is the passivation layer shape of the present invention The heat treatment thing (burned material) of one-tenth compositions；Be configured at above-mentioned semiconductor substrate selected from above-mentioned p-type layer and above-mentioned n-layer In the layer of more than 1 on electrode.Above-mentioned solar cell device can have other element the most further.

Above-mentioned solar cell device is formed, by the passivation layer of the present invention, the passivation layer formed by compositions by having, from And make conversion efficiency excellent.

As the semiconductor substrate of imparting passivation layer formation compositions, there is no particular restriction, can be according to purpose from logical The semiconductor substrate often used suitably selects.As semiconductor substrate, it is possible to use at the quasiconductor of band passivation layer The semiconductor substrate of explanation in substrate, it is possible to the semiconductor substrate being preferably used is too.The quasiconductor of above-mentioned passivation layer is set The face of substrate both can be p-type layer, it is also possible to be n-layer.Wherein, from the viewpoint of conversion efficiency, preferably p-type layer.On State the p-type layer on semiconductor substrate and both can be derived from the p-type layer of p-type semiconductor substrate, it is also possible to be with p-diffusion layer or p⁺The form of type diffusion layer is formed at the p-type layer on n-type semiconductor substrate or p-type semiconductor substrate.Additionally, arrange above-mentioned passivation The sensitive surface that the face of the semiconductor substrate of layer is preferably in solar cell device.

There is no particular restriction for the thickness of above-mentioned semiconductor substrate, suitably can select according to purpose.Such as can set It is 50 μm～1000 μm, preferably 75 μm～750 μm.

Additionally, the thickness of the passivation layer being formed on above-mentioned semiconductor substrate there is no particular restriction, can enter according to purpose Row suitably selects.The average thickness of such as passivation layer is preferably 5nm～50 μm, more preferably 10nm～30 μm, further preferably For 15nm～20 μm.

For the shape of above-mentioned solar cell device, size etc. unrestricted.For example, it is preferable to for the length of side be 125mm～ The square of 156mm.

The manufacture method of the solar cell device of the present invention, comprising: form having to engage p-type layer and n-layer Pn-junction and have on the layer of more than 1 in p-type layer and n-layer electrode semiconductor substrate, there is above-mentioned electricity The face of pole at least some of, gives the passivation layer formation compositions of the present invention and forms the operation of composition layer；With to upper State composition layer to carry out heat treatment (burning till) and form the operation of passivation layer.The manufacture method of above-mentioned solar cell device is permissible There is other operation the most further.

By using above-mentioned passivation layer formation compositions, it is possible to possess with easy method manufacture and there is excellent passivation effect Fruit and the big passivation layer of refractive index and the excellent solar cell device of conversion efficiency.And then, electrode can be formed with Forming passivation layer according to required form on semiconductor substrate, the productivity ratio making solar cell device is excellent.

Semiconductor substrate that be configured with electrode on the layer of at least one party in p-type layer and n-layer, that have pn-junction is permissible Commonly used method is utilized to manufacture.Such as, the desired zone at semiconductor substrate gives the electrodes such as silver paste agent, Aluminum Paste Formation paste, and carry out heat treatment (burning till) as required, thus can manufacture this semiconductor substrate.

The face of the semiconductor substrate arranging above-mentioned passivation layer both can be p-type layer, it is also possible to be n-layer.Wherein, from conversion From the viewpoint of efficiency, preferably p-type layer.

Use above-mentioned passivation layer formation compositions and form the details of the method for passivation layer and described The manufacture method of the semiconductor substrate with passivation layer is identical, and preferred mode is the most identical.

There is no particular restriction for the thickness of the passivation layer being formed on above-mentioned semiconductor substrate, can carry out suitably according to purpose Select.The average thickness of such as passivation layer is preferably 5nm～50 μm, more preferably 10nm～30 μm, more preferably 15nm ～20 μm.

Referring to the drawings embodiments of the present invention are illustrated.

(a) of Fig. 1～(d) of Fig. 1 are to have passivation layer too with what sectional view form schematically showed present embodiment The process chart of one example of the manufacture method of sun energy cell device.But, this process chart does not has any restriction to the present invention.

As shown in (a) of Fig. 1, the near surface at p-type semiconductor substrate 1 forms n⁺Type diffusion layer 2, and in most surface Form antireflection film 3.As antireflection film 3, silicon nitride film, oxidation titanium film etc. can be enumerated.In antireflection film 3 and p-type semiconductor The surface protection film (not shown) of silicon oxide etc. can be there is further between substrate 1.Additionally, due to the passivation layer of the present invention Refractive index is relatively big, the most preferably forms this passivation layer (not shown) between antireflection film 3 and p-type semiconductor substrate 1.Although In (a) of Fig. 1～(d) of Fig. 1, do not make diagram, but Fig. 3 will be used to have passivation layer in sensitive surface side below The manufacture method of solar cell device describes.

Then, as shown in (b) of Fig. 1, it is coated with aluminum electrode paste agent in a part of region at the back side of p-type semiconductor substrate 1 After material Deng formation backplate 5, carry out heat treatment (burning till) and form backplate 5, and make aluminum atoms permeating to p-type Semiconductor substrate 1 forms p⁺Type diffusion layer 4.

Then, as shown in (c) of Fig. 1, after the sensitive surface side coating electrode formation paste of p-type semiconductor substrate 1, enter Row heat treatment (burning till) and form sensitive surface electrode 7.By using containing the glass dust with burn through (fire through) property The material at end as electrode formation paste, can as shown in (c) of Fig. 1 through antireflection film 3, and at n⁺Type diffusion layer Form sensitive surface electrode 7 on 2 and obtain Ohmic contact.

It addition, in (a) of Fig. 1～(d) of Fig. 1, (b) of Fig. 1 and (c) of Fig. 1 are entered as the most independent operation Go diagram but it also may the operation of (b) of Fig. 1 and (c) of Fig. 1 is merged into 1 operation.Specifically, can be above-mentioned After in (b) of Fig. 1, a part of region coating aluminum electrode paste agent etc. overleaf forms the material of backplate 5 and carry out for shape Before becoming the heat treatment (burning till) of backplate 5, electrode formation paste is coated on sensitive surface side, then carries out in this stage Heat treatment (burns till).In the case of the method, 1 heat treatment is utilized to form the electrode of the back side and sensitive surface to simplify operation.

Then, as shown in (d) of Fig. 1, the back side p-type layer in addition to being formed with the region of backplate 5 give blunt Change layer formation compositions and form composition layer.Imparting can be carried out by methods such as such as silk screen printings.To being formed at p Composition layer on type layer carries out heat treatment (burning till) and forms passivation layer 6.By being formed by above-mentioned passivation in p-type layer overleaf The passivation layer 6 that layer formation is formed by compositions, can manufacture the solar cell device that generating efficiency is excellent.

In the solaode unit utilizing the manufacture method including manufacturing process shown in (a) of Fig. 1～(d) of Fig. 1 to manufacture In part, aluminum etc. the backplate formed can be made point cantact structure, and the warpage etc. of substrate can be reduced.And then, By using above-mentioned passivation layer formation compositions, it is possible to only in specific position (specifically except the district being formed with electrode In p-type layer beyond territory) form passivation layer with excellent productivity ratio.

Additionally, (d) of Fig. 1 shows the method only forming passivation layer at the back portion of semiconductor substrate 1, but also may be used Also give passivation layer formation compositions with the side in addition to rear side at semiconductor substrate 1 and it is carried out heat treatment (burning till), thus also form passivation layer 6 (not shown) in the side (edge) of semiconductor substrate 1.Thereby, it is possible to manufacture generating effect The solar cell device that rate is more excellent.

Further, it is also possible to part is formed without passivation layer and is only coated with the passivation layer formation group of the present invention in side overleaf Compound also carries out heat treatment (burning till) to it, thus forms passivation layer.The passivation layer formation compositions of the present invention is for picture During the many position of crystal defect as side, its effect is the biggest.

The mode forming passivation layer after electrode is formed is illustrated by (a) of Fig. 1～(d) of Fig. 1 but it also may Wait the electrode forming aluminum etc. in required region further with evaporation after forming passivation layer.

(a) of Fig. 2～(e) of Fig. 2 are the tools of the present embodiment schematically showing the present invention with sectional view form There is the process chart of another example of the manufacture method of the solar cell device of passivation layer.Specifically, (a) of Fig. 2～Fig. 2 E () is the process chart including following operation with the explanation of sectional view form: use aluminum electrode paste agent or can utilize at thermal diffusion Reason forms p⁺The p-diffusion layer formation compositions of type diffusion layer forms p⁺After type diffusion layer, remove at the heat of aluminum electrode paste agent Reason thing or p⁺The heat treatment thing of type diffusion layer formation compositions.Here, as p-diffusion layer formation compositions, such as may be used Enumerate containing the compositions containing recipient element material and glass ingredient.

As shown in (a) of Fig. 2, the near surface at p-type semiconductor substrate 1 forms n⁺Type diffusion layer 2, and formed on surface Antireflection film 3.As antireflection film 3, silicon nitride film, oxidation titanium film etc. can be enumerated.

Then, as shown in (b) of Fig. 2, a part of region overleaf gives p⁺After type diffusion layer formation compositions, enter Row heat treatment and form p⁺Type diffusion layer 4.At p⁺P is formed on type diffusion layer 4⁺The heat treatment thing of type diffusion layer formation compositions 8。

Here, aluminum electrode paste agent can be used to replace p-diffusion layer formation compositions.In the feelings using aluminum electrode paste agent Under condition, at p⁺Aluminum electrode 8 is formed on type diffusion layer 4.

Then, as shown in (c) of Fig. 2, utilize the methods such as etching to remove and be formed at p⁺P-diffusion layer on type diffusion layer 4 The heat treatment thing 8 of formation compositions or aluminum electrode 8.

Then, as shown in (d) of Fig. 2, at sensitive surface (surface) and a part of regional choice at the back side of semiconductor substrate 1 Property ground coating electrode formation paste after, carry out heat treatment and form sensitive surface electrode 7 at sensitive surface (surface), and overleaf Form backplate 5.By using the material containing the glass powder with burn through as the electrode coating sensitive surface side Formation paste, can as shown in (d) of Fig. 2 through antireflection film 3, and at n⁺Sensitive surface electricity is formed on type diffusion layer 2 Pole 7 and obtain Ohmic contact.

Additionally, due to formed p in the region forming backplate⁺Type diffusion layer 4, thus be accordingly used in formation backplate The electrode formation paste of 5 is not limited to aluminum electrode paste agent, it is possible to use silver electrode paste etc. can form more low resistance The electrode paste of electrode.Thus, it is also possible to improve generating efficiency further.

Then, as shown in (e) of Fig. 2, the back side p-type layer in addition to being formed with the region of backplate 5 give blunt Change layer formation compositions and form composition layer.Imparting can be carried out by methods such as such as silk screen printings.To being formed at p Composition layer on type layer carries out heat treatment (burning till) and forms passivation layer 6.By being formed by the present invention in p-type layer overleaf The passivation layer 6 that formed by compositions of passivation layer formation, the solar cell device that generating efficiency is excellent can be manufactured.

Additionally, the method only forming passivation layer at the back portion of semiconductor substrate 1 shown in (e) of Fig. 2 but it also may Also give passivation layer formation material in the side in addition to rear side of p-type semiconductor substrate 1 and it is carried out heat treatment (burning Become), thus also form passivation layer (not shown) in the side (edge) of p-type semiconductor substrate 1.Thereby, it is possible to manufacture generating effect The solar cell device that rate is more excellent.

Further, it is also possible to part is formed without passivation layer and only gives the blunt of the present invention in the side of semiconductor substrate overleaf Change layer formation compositions and it is carried out heat treatment (burning till), thus forming passivation layer.The passivation layer formation group of the present invention Compound is when the position many for crystal defect as image side surface, and its effect is the biggest.

The mode forming passivation layer after electrode is formed is illustrated by (a) of Fig. 2～(e) of Fig. 2 but it also may Wait the electrode forming aluminum etc. in required region further with evaporation after forming passivation layer.

It is formed with n at sensitive surface in the above-described embodiment to using⁺The situation of the p-type semiconductor substrate of type diffusion layer is entered Go explanation, but used and be formed with p at sensitive surface⁺In the case of the n-type semiconductor substrate of type diffusion layer, it is also possible to similarly make Make solar cell device.It should be noted that now, side forms n overleaf⁺Type diffusion layer.

And then, passivation layer formation compositions can be used for being formed side the most overleaf and is configured with electricity The sensitive surface side of the back electrode type solar cell device of pole or the passivation layer 6 of rear side.

As shown in the schematic cross sectional views of Fig. 3, the near surface in the sensitive surface side of p-type semiconductor substrate 1 forms n⁺Type Diffusion layer 2, and passivation layer 6 and antireflection film 3 is formed on its surface.As antireflection film 3, it is known that silicon nitride film, oxidation titanium film Deng.Additionally, passivation layer 6 is by giving the passivation layer formation compositions of the present invention and it is carried out heat treatment (burning till) carrying out shape Become.Owing to the passivation layer of the present invention shows good refractive index, it is taken as that can be by this passivation layer is arranged on sensitive surface Generating efficiency is improved in side.

P in the rear side of p-type semiconductor substrate 1⁺Type diffusion layer 4 and n⁺Backplate 5 it is respectively provided with on type diffusion layer 2, And then the region not forming electrode overleaf arranges passivation layer 6.

p⁺Type diffusion layer 4 can be as described above by desired zone coating p-diffusion layer formation compositions or aluminum After electrode paste agent, it is carried out heat treatment to be formed.Additionally, n⁺Type diffusion layer 2 can be by such as at required region coating energy Heat diffusion treatment is enough utilized to form n⁺After the n-type diffusion layer formation compositions of type diffusion layer, it is carried out heat treatment to be formed.

Here, as n-type diffusion layer formation compositions, include, for example containing containing donor element material and glass ingredient Compositions.

It is separately positioned on p⁺Backplate 5 on type diffusion layer 4 and n+ type diffusion layer 2 can be by using silver electrode paste Formed etc. normally used electrode formation paste.

Additionally, be arranged on p⁺Backplate 5 on type diffusion layer 4 can also be for using aluminum electrode paste agent and p⁺Type diffusion layer 4 The aluminum electrode formed together.

The passivation layer 6 being arranged on the back side can be by giving passivation layer formation group in the region being not provided with backplate 5 Compound also carries out heat treatment (burning till) to it and is formed.

Additionally, passivation layer 6 is possible not only to be formed at the back side of semiconductor substrate 1, and it is additionally formed in side and (does not schemes Show).

In the back electrode type solar cell device shown in Fig. 3, owing to not there is electrode in sensitive surface side, therefore send out Electrical efficiency is excellent.And then, owing to the region not forming electrode overleaf forms passivation layer, therefore make conversion efficiency more excellent.

Illustrated above use p-type semiconductor substrate as the example of semiconductor substrate, but use n-type semiconductor substrate Time can also manufacture, according to above-mentioned, the solar cell device that conversion efficiency is excellent.For solar cell device shape, Size is the most unrestricted, and the most common length of side is the square of 125mm～156mm.

Solaode has the solar cell device of the present invention and is configured at the electrode of above-mentioned solar cell device On wiring material.Solaode can also connect multiple solaodes unit by wiring materials such as lug lines as required Part also utilizes encapsulant to seal.

As above-mentioned wiring material and encapsulant, there is no particular restriction, can be from the normally used material of the art Material suitably selects.

Size for above-mentioned solaode is the most unrestricted.Solaode be preferably sized to 0.5m²～3m²。

Embodiment

Hereinafter, utilize embodiment that the present invention is further illustrated, but the present invention is not limited to the examples. It addition, as long as no special declaration, then " % " is quality criteria.

(passivation layer is formed with the preparation of compositions 1)

By ethyl cellulose (being evolved into Co., Ltd., trade name: ETHOCEL200cps day) 5.00g and terpinol (NIPPON TERPENE CHEMICALS, INC.) 95.02g mixes, and stirs 1 hour, be prepared as ethyl cellulose at 150 DEG C Solution.

Then, by oacetic acid aluminum-diisopropoxide (Kawaken Fine Chemicals Co., Ltd., trade name: ALCH) 15.1g, ethanol niobium (Wako Pure Chemical Industries, Ltd.) 5.1g, titanium tetraisopropylate (Wako Pure Chemical Industries, Ltd.) 5.0g, above-mentioned ethyl cellulose solution 35.2g and terpinol (NIPPON TERPENE CHEMICALS, INC.) 30.2g mixing, It is prepared as passivation layer formation compositions 1.

(formation of passivation layer)

(SUMCO Co., Ltd. system, 50mm be square, thickness: 625 for the monocrystalline type p-type silicon substrate using surface to be mirror shape μm) as semiconductor substrate.Use RCA cleaning mixture (Kanto Kagaku K. K., trade name: Frontier Cleaner-A01) By silicon substrate dipping washing 5 minutes at 70 DEG C, thus carry out pre-treatment.

Then, use silk screen print method, reach silica-based through pre-treatment of the mode of 5 μm according to making dried thickness The upper passivation layer formation compositions 1 giving above-mentioned acquisition of whole of plate, carries out 5 minutes dried at 150 DEG C.Then, After carrying out 10 minutes heat treatment (burning till) at 700 DEG C, at room temperature place cooling, be thus fabricated to evaluation substrate.

The evaluation substrate being fabricated to passivation layer formation compositions obtained above and use said composition is carried out Following evaluation, and evaluation result is shown in table 1.

(evaluation of thixotropic ratio)

Rotary shear viscosity meter (AntonPaar company, trade name: MCR301) installs cone-plate (diameter 50mm, cone 1 ° of angle), and in temperature 25 DEG C, shear rate 1.0s^-1And 10s^-1Under conditions of respectively to upper (within 12 hours) immediately after preparation The shear viscosity stating prepared passivation layer formation compositions 1 is determined.

It is 1.0s in shear rate^-Shear viscosity (η under conditions of 1₁) it is 44.0Pa s, it is 10s in shear rate^-1 Under conditions of shear viscosity (η₂) it is 35.0Pa s.Shear viscosity is 1.0s^-1And 10s^-1Time thixotropic ratio (η₁/η₂) it is 1.3。

(evaluation of storage stability)

After (within 12 hours) and preserving 30 days at 25 DEG C immediately after preparation, respectively to above-mentioned prepared passivation layer shape The shear viscosity of one-tenth compositions 1 is determined.MCR301 (trade name, AntonPaar company) installs cone-plate (diameter 50mm, cone angle 1 °), and in temperature 25 DEG C, shear rate 1.0s^-1Under carried out the mensuration of shear viscosity.

Shear viscosity (the η at 25 DEG C immediately after preparation₀) it is 44.0Pa s, at 25 DEG C after preserving 30 days at 25 DEG C Shear viscosity (η₃₀) it is 44.6Pa s.

The rate of change of the shear viscosity after preserving 30 days at 25 DEG C is calculated according to following formula (B), and according to following evaluation Storage stability is evaluated by benchmark.

Rate of change (%)=(η of shear viscosity₃₀-η₀)/(η₀)×100 (B)

[metewand]

The rate of change of A: shear viscosity is less than 10%.

The rate of change of B: shear viscosity is 10% less than 30%.

The rate of change of C: shear viscosity is more than 30%.

If being evaluated as A or B, then as being good for passivation layer formation compositions.

(mensuration of useful life)

Determinator in service life (Japan Shi Meilebo Co., Ltd., trade name: WT-2000PVN), at room temperature (25 DEG C) Lower utilize Photoconductivity decay by microwave reflectance damped method that the useful life (μ s) of the evaluation substrate of above-mentioned acquisition is determined.Obtained The useful life in the region imparting semiconductor substrate passivation layer formation compositions of the evaluation substrate obtained is 300 μ s.

(thickness of passivation layer and the mensuration of refractive index)

Use interference formula film thickness gauge (FILMETRICS Co., Ltd., F20 determining film thickness system) to evaluation obtained above Average thickness and refractive index with the passivation layer on substrate are determined.The thickness of passivation layer is 220nm, and refractive index is 1.71。

(passivation layer is formed with the preparation of compositions 2)

By oacetic acid aluminum-diisopropoxide 14.9g, titanium tetraisopropylate 9.8g, above-mentioned ethyl cellulose solution 35.1g And terpinol 29.7g mixing, it is prepared as passivation layer formation compositions 2.

In addition to using passivation layer formation by compositions 2, evaluated similarly to Example 1, shown the result in In table 1.

(passivation layer is formed with the preparation of compositions 3)

By oacetic acid aluminum-diisopropoxide 15.0g, ethanol zirconium (Wako Pure Chemical Industries, Ltd.) 10.2g, above-mentioned Ethyl cellulose solution 35.1g and terpinol 30.4g mixing, is prepared as passivation layer formation compositions 3.

In addition to using passivation layer formation by compositions 3, evaluated similarly to Example 1, shown the result in In table 1.

(passivation layer is formed with the preparation of compositions 4)

By oacetic acid aluminum-diisopropoxide 15.2g, ethanol niobium 10.0g, titanium ethanolate 5.1g, tetraethyl orthosilicate (with Wako Pure Chemical Industries Co., Ltd.) 4.8g, above-mentioned ethyl cellulose solution 34.7g and terpinol 30.3g mixing, be prepared as passivation layer Formed by compositions 4.

In addition to using passivation layer formation by compositions 4, evaluated similarly to Example 1, shown the result in In table 1.

(passivation layer is formed with the preparation of compositions 5)

By oacetic acid aluminum-diisopropoxide 14.9g, titanium ethanolate 15.2g, tetraethyl orthosilicate 5.2g, above-mentioned ethyl fibre Dimension cellulose solution 34.8g and terpinol 30.6g mixing, is prepared as passivation layer formation compositions 5.

In addition to using passivation layer formation by compositions 5, evaluated similarly to Example 1, shown the result in In table 1.

(passivation layer is formed with the preparation of compositions 6)

By oacetic acid aluminum-diisopropoxide 15.0g, ethanol zirconium 15.1g, tetraethyl orthosilicate 5.1g, above-mentioned ethyl fibre Dimension cellulose solution 35.3g and terpinol 29.6g mixing, is prepared as passivation layer formation compositions 6.

In addition to using passivation layer formation by compositions 6, evaluated similarly to Example 1, shown the result in In table 1.

(passivation layer is formed with the preparation of compositions 7)

By oacetic acid aluminum-diisopropoxide 15.1g, ethanol niobium 5.0g, isopropyl titanate 5.0g, isobornyl cyclohexanol (NIPPON TERPENE CHEMICALS, INC., trade name: Terusolve MTPH) 35.2g and terpinol 14.9g mixing, It is prepared as passivation layer formation compositions 7.

In addition to using passivation layer formation by compositions 7, evaluated similarly to Example 1, shown the result in In table 1.It addition, thixotropic ratio is with shear rate as 1.0s^-1Time shear viscosity (η₁) with shear rate be 1000s^-1Time shearing Viscosity (η₃) ratio (η₁/η₃) form calculate.

(passivation layer is formed with the preparation of compositions 8)

By oacetic acid aluminum-diisopropoxide 15.2g, isopropyl titanate 10.2g, isobornyl cyclohexanol 34.8g and terpin Alcohol 15.2g mixes, and is prepared as passivation layer formation compositions 8.

In addition to using passivation layer formation by compositions 8, evaluated together with embodiment 1, shown the result in table 1 In.It addition, thixotropic ratio is with shear rate as 1.0s^-1Time shear viscosity (η₁) with shear rate be 1000s^-1Time shear viscosity (η₃) ratio (η₁/η₃) form calculate.

(passivation layer is formed with the preparation of compositions 9)

By oacetic acid aluminum-diisopropoxide 14.8g, ethanol zirconium 9.8g, isobornyl cyclohexanol 35.5g and terpinol 15.2g mixes, and is prepared as passivation layer formation compositions 9.

In addition to using passivation layer formation by compositions 9, evaluated similarly to Example 1, shown the result in In table 1.It addition, thixotropic ratio is with shear rate as 1.0s^-1Time shear viscosity (η₁) with shear rate be 1000s^-1Time shearing Viscosity (η₃) ratio (η₁/η₃) form calculate.

(passivation layer is formed with the preparation of compositions 10)

Oacetic acid aluminum-diisopropoxide 15.0g, above-mentioned ethyl cellulose solution 35.0g and terpinol 30.2g are mixed Close, be prepared as passivation layer formation compositions 10.

In addition to using passivation layer formation by compositions 10, evaluated similarly to Example 1, shown the result in In table 1.

(passivation layer is formed with the preparation of compositions 11)

Oacetic acid aluminum-diisopropoxide 15.1g, isobornyl cyclohexanol 34.9g and terpinol 15.2g are mixed, system Standby one-tenth passivation layer is formed by compositions 11.

In addition to using passivation layer formation by compositions 11, evaluated similarly to Example 1, shown the result in In table 1.It addition, thixotropic ratio is with shear rate as 1.0s^-1Time shear viscosity (η₁) with shear rate be 1000s^-1Time shearing Viscosity (η₃) ratio (η₁/η₃) form calculate.

[table 1]

As known from the above, the passivation layer formation compositions of the application of the invention, it is possible to formed and there is excellent passivation effect Fruit and the big passivation layer of refractive index.In addition understand, the excellent storage stability of the passivation layer formation compositions of the present invention.And then Understand, the passivation layer formation compositions of the application of the invention, it is possible to form the passivation layer of required form with easy operation.

It addition, for Japanese patent application 2012-156472 and the disclosure of Japanese patent application 2012-218389, Using its entirety as with reference to being incorporated in this specification.

Whole documents, patent application and technical standard described in this specification, and specifically and respectively describes each The situation of document, patent application and technical standard is quoted in this specification as reference with degree.

Claims

1. a passivation layer formation compositions, its comprise the organo-aluminum compound shown in following logical formula (I) and selected from titanium alkoxide, At least one alkoxide compound in zirconium alkoxides and silicon alkoxide,

In logical formula (I), R¹Separately representing the alkyl of carbon number 1～8, n represents the integer of 0～3, X²And X³Separately Represent oxygen atom or methylene, R²、R³And R⁴Separately represent hydrogen atom or the alkyl of carbon number 1～8.

Passivation layer formation compositions the most according to claim 1, it also comprises alkanol niobium.

Passivation layer formation compositions the most according to claim 2, wherein, described alkanol niobium is selected from ethanol niobium, isopropyl At least one in alcohol niobium, normal propyl alcohol niobium, n-butyl alcohol niobium and phenol niobium.

4. according to the passivation layer formation compositions according to any one of claims 1 to 3, wherein, described alkoxide compound Including at least described titanium alkoxide, described titanium alkoxide be selected from methanol titanium, titanium ethanolate, isopropyl titanate, normal propyl alcohol titanium, n-butyl titanium, At least one in tert-butyl alcohol titanium, titanium isobutoxide, diisopropoxy bis-acetylacetonate titanium and four (2-ethyl-1-hexanol) titanium.

5. according to the passivation layer formation compositions according to any one of claims 1 to 3, wherein, described alkoxide compound Including at least described zirconium alkoxides, described zirconium alkoxides is selected from ethanol zirconium, zirconium iso-propoxide, zirconium-n-propylate, zirconium-n-butylate, the tert-butyl alcohol At least one in zirconium, acetylacetone,2,4-pentanedione zirconium, trifluoroacetylacetone (TFA) zirconium and hexafluoroacetylacetone zirconium.

6. according to the passivation layer formation compositions according to any one of claims 1 to 3, wherein, described alkoxide compound Including at least described silicon alkoxide, described silicon alkoxide is the silicon alkoxide shown in following logical formula (II),

(R⁵O)_(4-m)SiR⁶ _m (II)

In logical formula (II), R⁵And R⁶Separately representing the alkyl of carbon number 1～8, m represents the integer of 0～3.

7., according to the passivation layer formation compositions according to any one of claims 1 to 3, it also comprises resin.

8., according to the passivation layer formation compositions according to any one of claims 1 to 3, it also comprises following logical formula (III) Shown compound

9. a semiconductor substrate for band passivation layer, it has semiconductor substrate and whole be arranged on described semiconductor substrate Or the passivation layer of a part, described passivation layer is the heat of the passivation layer formation compositions according to any one of claim 1～8 Processed material.

10. a manufacture method for the semiconductor substrate of band passivation layer, comprising:

On semiconductor substrate whole or a part of entitle are required the passivation layer formation group according to any one of 1～8 Compound and form the operation of composition layer；With

Described composition layer is carried out heat treatment and forms the operation of passivation layer.

11. 1 kinds of solar cell devices, it has:

P-type layer and n-layer are carried out the semiconductor substrate that pn engages；

Whole or the passivation layer of a part being arranged on described semiconductor substrate, described passivation layer is to appoint in claim 1～8 The heat treatment thing of one described passivation layer formation compositions；With

Electrode on the layer of be configured at described semiconductor substrate more than in described p-type layer and n-layer 1.

The manufacture method of 12. 1 kinds of solar cell devices, comprising:

To there is pn-junction p-type layer and n-layer engaged and more than 1 in described p-type layer and described n-layer Layer on there is the semiconductor substrate, the face with described electrode at least some of of electrode, entitle requires in 1～8 Passivation layer formation compositions described in any one and form the operation of composition layer；With

13. 1 kinds of solaodes, it has the solar cell device described in claim 11 and is configured at described solar energy Wiring material on the electrode of cell device.