WO2018040990A1 - 聚硅氧烷、半导体用材料、半导体及太阳能电池制备方法 - Google Patents

聚硅氧烷、半导体用材料、半导体及太阳能电池制备方法 Download PDF

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WO2018040990A1
WO2018040990A1 PCT/CN2017/098627 CN2017098627W WO2018040990A1 WO 2018040990 A1 WO2018040990 A1 WO 2018040990A1 CN 2017098627 W CN2017098627 W CN 2017098627W WO 2018040990 A1 WO2018040990 A1 WO 2018040990A1
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type impurity
polysiloxane
semiconductor
semiconductor substrate
impurity diffusion
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French (fr)
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徐芳荣
李平
池田武史
宋韡
金光男
梅原正明
北田刚
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Toray Advanced Materials Research Laboratories China Co Ltd
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Toray Advanced Materials Research Laboratories China Co Ltd
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Priority claimed from CN201610787302.7A external-priority patent/CN107793570A/zh
Priority claimed from CN201610787280.4A external-priority patent/CN107793569A/zh
Application filed by Toray Advanced Materials Research Laboratories China Co Ltd filed Critical Toray Advanced Materials Research Laboratories China Co Ltd
Priority to EP17845292.6A priority Critical patent/EP3508514B1/en
Priority to KR1020197002484A priority patent/KR102225181B1/ko
Priority to CN201780015761.6A priority patent/CN109153787B/zh
Priority to JP2018564210A priority patent/JP7163774B2/ja
Priority to US16/314,493 priority patent/US10738218B2/en
Publication of WO2018040990A1 publication Critical patent/WO2018040990A1/zh
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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Definitions

  • the present invention relates to polysiloxanes, materials for solar energy and semiconductors, methods of preparing semiconductor units, and solar cells. Specifically, it relates to a series of organic synthesis of polysiloxanes, doping materials for solar and semiconductors, and mask materials, methods of preparing semiconductor units using the materials, and solar cells.
  • a process of diffusing p-type and n-type impurities in a semiconductor substrate used in a solar cell to form an impurity diffusion layer, respectively, for p-type impurity diffusion employ different processes.
  • such a method has a problem that the number of processes increases.
  • it has been proposed to impart a p-type impurity diffusion composition containing an acceptor element on a semiconductor substrate, and heat-treating the shape. After the p-type impurity diffusion layer is formed, a part of the heat-treated material of the p-type impurity diffusion composition is used as a mask to form an n-type impurity diffusion layer.
  • gas dopants are generally highly toxic substances such as boron tribromide, phosphine, and phosphorus oxychloride.
  • the requirements for pipelines and exhaust gas absorption equipment are high, and once a leak occurs, there is a possibility of a major accident and the surrounding environment. Produce pollution.
  • Patent Literature [1] Wei Qingzhu, Lu Junyu, Lian Weifei, Ni Zhichun, N-type double-sided battery and its manufacturing method: China, CN201510020649.4[P].2015-01-15.[1]
  • the present invention provides a polysiloxane, and a material for solar energy and semiconductor prepared using the polysiloxane, and also provides a semiconductor unit using the material for a solar cell and a semiconductor, and a manufacturing process of the solar cell .
  • the present invention discloses a polysiloxane containing at least one molecular structure fragment selected from the following formula 1,
  • Q is an alkyl group having an alcoholic hydroxyl group and having a main chain carbon number of less than 12, or an alkyl group having an alcoholic hydroxyl group and having a main chain non-hydrogen atom number of less than 12 and containing a hetero atom
  • T is a hydroxyl group, an alkyl group, or a An alkyl group having an alcoholic hydroxyl group and having a main chain carbon number of less than 12, or an alkyl group having an alcoholic hydroxyl group and having a main chain non-hydrogen atom number of less than 12 and containing a hetero atom.
  • the Q is preferably a structural fragment represented by the formula 2,
  • X is an alkyl group having a carbon number of less than 7, or an alkyl group having a main chain having a non-hydrogen atom number of less than 7 and containing a hetero atom; and R 1 , R 2 and R 3 are each independently a hydrogen atom and a carbon atom; A substituent of less than 3, or R 2 is bonded to a carbon atom on X to form a cyclic substituent.
  • the X is preferably a main chain having a non-hydrogen atom number of less than 7 and containing a hetero atom in order to make the polysiloxane susceptible to thermal decomposition and to make the silicon content capable of achieving barrier properties and inhibiting diffusion in the gas. alkyl.
  • in-gas diffusion means that during the diffusion process, the dopant component in the dopant slurry or mask material volatilizes into the gas surrounding it and diffuses in the gas.
  • R 1 , R 2 , and R 3 are each independently a hydrogen atom and have a carbon number of 1 due to solubility in water and a requirement to ensure that the silicon content can achieve barrier properties and inhibit gas diffusion.
  • a substituent or R 2 is bonded to a carbon atom on X to form a cyclic substituent. Further preferably, each of R 1 , R 2 and R 3 is independently a hydrogen atom.
  • the polysiloxane preferably further contains at least one molecular structure fragment selected from the following formula 3 in a molar content of from 1 to 99%.
  • X1 is an alkyl group having a carbon number of less than 8, or an aryl group having a carbon number of less than 10; and Y1 is a hydroxyl group, an aryl group having a carbon number of less than 10, or an alkyl group having a carbon number of less than 8.
  • the solubility in water is maintained to some extent in addition to the solubility in an organic solvent, and the molecular structure fragment represented by Formula 2 preferably has a molar content of from 1 to 50%.
  • the Y1 is preferably a hydroxyl group for the consideration of cost and consideration of maintaining the solubility in water by utilizing the hydrophilicity of a hydroxyl group.
  • T is a hydroxyl group, an alkyl group having a carbon number of less than 8, or a structure represented by Formula 4.
  • Z is an alkyl group having a carbon number of less than 7, or an alkyl group having a main chain having a non-hydrogen atom number of less than 7 and containing a hetero atom; and R1, R2 and R3 are each independently a hydrogen atom and a carbon number of less than 3
  • the group, or R5, is bonded to a carbon atom on Z to form a cyclic substituent.
  • the Z is preferably a main chain having a non-hydrogen atom number of less than 7 and containing a hetero atom in order to make the polysiloxane easy to thermally decompose and to make the silicon content capable of achieving barrier properties and inhibiting diffusion in the gas.
  • Alkyl a main chain having a non-hydrogen atom number of less than 7 and containing a hetero atom in order to make the polysiloxane easy to thermally decompose and to make the silicon content capable of achieving barrier properties and inhibiting diffusion in the gas.
  • the T is preferably a hydroxyl group in view of the requirement that the silicon content in the polysiloxane can achieve barrier properties and inhibit the diffusion in the gas.
  • the polysiloxane does not contain an ethylene oxide structure.
  • the polysiloxane is preferably composed only of the molecular structure fragment represented by Formula 1 in which Q is a molecular structure fragment represented by Formula 2.
  • the molecular structure fragments are preferably the same molecular structure fragments.
  • the polysiloxane has a weight average molecular weight of 500 to 50,000.
  • the polysiloxane preferably has a weight average molecular weight of from 1,000 to 11,000 for the purpose of not causing local unevenness even if the molecular weight is increased during storage.
  • the polysiloxane preferably has a weight average molecular weight of 1,500 to 5,500 in view of extending the shelf life.
  • the polysiloxane of the present invention is not particularly limited, and specific examples thereof are as follows.
  • the actual arrangement of the repeating unit structure is not limited to the following structural examples.
  • the present invention also discloses a material for solar energy and a semiconductor (hereinafter, also simply referred to as "the material of the present invention"), which contains the polysiloxane described above.
  • the material for solar energy and semiconductor may further include: dopant component A, polymer binder B, and solvent C.
  • the materials for solar energy and semiconductor of the present invention may also be free of dopant component A when used as a mask material.
  • the dopant component A is not particularly limited, and it is preferable that the dopant component A is an n-type dopant component of a compound containing a fifth main group element or a compound containing a third main group element. P-type dopant component.
  • the dopant component A preferably contains an inorganic boron compound component or an inorganic phosphorus compound component because of low cost and abundant sources.
  • the inorganic boron compound contained in the dopant component A is boron trioxide or boric acid, and the inorganic phosphorus compound is phosphoric acid, in view of safety and low cost of use.
  • the molecular structure repeating unit of the polymer binder B contains an alcoholic hydroxyl group.
  • the polymer binder B has a weight average molecular weight ranging from 1,000 to 300,000. It is further preferred that the polymer binder B has a weight average molecular weight ranging from 3,000 to 50,000 in view of ease of thermal decomposition and application to spin coating.
  • the polymer binder is not particularly limited, and polyacryl alcohol or polyvinyl alcohol is preferred.
  • the solvent C be composed of 0 to 50% of water and 50 to 100% of an organic solvent.
  • the organic solvent is preferably an organic solvent having a boiling point of 50 to 300 degrees Celsius.
  • the organic solvent is not particularly limited, and preferably 1-methoxy-2-propanol, diacetone alcohol, 2-propanol, n-butanol, 3-methoxy-3-methylbutanol, diethylene glycol Methyl ether, propylene glycol, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, alpha-terpineol, diethylene glycol monomethyl ether, diethylene glycol, methanol, ethanol, 1,4-dioxane Hexacyclic, acetone, methyl ethyl ketone, methyl lactate or ethyl lactate.
  • the total addition amount of the dopant component A, the polymer binder B, the polysiloxane, and the solvent C be relatively The total mass of the slurry is 2 to 30%.
  • the dopant component A, the polymer binder B, and the poly The total addition amount of the siloxane and the solvent C is 5 to 20% with respect to the total mass of the slurry.
  • the present invention also discloses a method of fabricating a semiconductor unit of a semiconductor substrate. It uses the aforementioned materials for solar energy and semiconductors.
  • the above method includes the following steps a to c,
  • a material of the present invention is applied as a first conductivity type impurity diffusion composition on one surface of each semiconductor substrate to form a first conductivity type impurity diffusion composition film,
  • the surfaces of the first semiconductor-type impurity-diffusion composition film in which the semiconductor substrates of the two sets are formed are opposed to each other.
  • the surfaces of the first semiconductor-type impurity diffusion composition film in which the two sets of the semiconductor substrates are formed are opposed to each other in order to reduce the contamination of the uncoated surface by the dopant component. And contamination of the diffusion surface of the first conductivity type impurity when the diffusion of the second conductivity type impurity is performed.
  • the step c is performed by using the heat treatment material of the first conductivity type impurity diffusion composition film as a mask after the step b.
  • the step c is performed continuously after the step b after the step b.
  • the heating temperature at the time of forming the second conductive type impurity diffusion layer in the step c is higher than the temperature at the time of forming the first conductive type impurity diffusion layer in the step b.
  • the semiconductor substrate In order to adjust the surface concentration of the first conductivity type and the second conductivity type impurity in the semiconductor substrate, it is preferable to further include a step of oxidizing the surface of the semiconductor substrate in an atmosphere containing oxygen.
  • the d process is performed continuously after the c process and after the c process.
  • the distance between the faces formed by the first conductivity type impurity diffusion composition film in each group is W1
  • the first conductivity type of the adjacent two groups is The distance between the film formation face of the impurity diffusion composition and the opposite surface thereof is W2, and W1 and W2 satisfy W1 ⁇ W2.
  • the impurity diffusion of the first conductivity type of the two sets of the semiconductor substrate was 0 mm.
  • the step b is an atmosphere containing oxygen. Go on.
  • the ratio of nitrogen gas to oxygen in the atmosphere in the above-described step b is the same as the ratio of nitrogen gas to oxygen in the atmosphere in the above-mentioned step c.
  • the first conductivity type is a p-type and the second conductivity type is an n-type.
  • the present invention also discloses a solar cell prepared according to the foregoing semiconductor unit manufacturing method.
  • the polysiloxane provided by the present invention not only has good solubility in an organic solvent, but also has improved solubility in water, and its application range is expanded.
  • a material for solar energy and semiconductor prepared by using the polysiloxane provided by the invention not only has good diffusibility, but also can reduce the cost to a certain extent, and also has good barrier property, and can also Suitable for mask materials with doping function.
  • the target result can be obtained without an additional mask layer, and the goal of shortening the process and reducing the cost is achieved.
  • the dopant-free material prepared using the polysiloxane provided by the present invention can be applied to a diffusion process in which doping is not desired at the mask.
  • the foregoing materials for solar energy and semiconductor can be further utilized, and the process not only utilizes excellent barrier properties and excellent diffusibility of the foregoing materials, but also The improvement of the manufacturing process further enhances the suppression of the diffusion of the dopant component A during doping to the region other than the material for solar energy and semiconductor coated in the present invention (ie, diffusion in the gas), shortening the number of processes and Process time.
  • Figure 1 shows the placement of silicon wafers for the barrier evaluation test.
  • Figure 2 shows the diffusion performance and the placement of the test wafer in the gas diffusion evaluation.
  • Fig. 3 is a schematic process sectional view showing an example of a method of manufacturing a semiconductor unit of the present invention, which is composed of Figs. 3i, 3ii and 3iii.
  • Fig. 3i is a cross-sectional view of a semiconductor substrate on which a first conductivity type impurity diffusion composition film is formed on one surface.
  • 3ii is a semiconductor substrate on which the first conductivity type impurity diffusion composition film is formed on the one surface A cross-sectional view of a placement in a diffusion boat.
  • Figure 3iii is a cross-sectional view of the semiconductor substrate of Figure 3ii after thermal diffusion.
  • FIG. 4 is a schematic cross-sectional view showing an example of the arrangement of the semiconductor substrate at the time of forming the first conductivity type impurity diffusion layer.
  • Fig. 5 is a schematic process sectional view showing an example of a method for producing a solar cell of the present invention, which is composed of Figs. 5i, 5ii, 5iii, 5iv, 5v, 5vi and 5vii.
  • Figure 5i is a cross-sectional view of an n-type semiconductor substrate.
  • Fig. 5ii is a cross-sectional view of a semiconductor substrate on which a p-type impurity diffusion composition film is formed on one surface.
  • Fig. 5iii is a cross-sectional view showing the p-type impurity diffusion of the semiconductor substrate of Fig. 5ii.
  • Figure 5iv is a cross-sectional view showing the diffusion of n-type impurities on the basis of Figure 5iii.
  • Fig. 5v is a cross-sectional view of the semiconductor substrate of Fig. 5iv after cleaning.
  • Fig. 5vi is a cross-sectional view showing the antireflection layer and the passivation layer formed on the semiconductor substrate of Fig. 5v.
  • Figure 5vii is a cross-sectional view of the electrode prepared on the semiconductor substrate of Figure 5vi.
  • Fig. 6 is a schematic cross-sectional view showing the arrangement of a semiconductor substrate on a diffusion boat of a comparative example.
  • the repeating unit structure of the polysiloxane of the present embodiment contains an alcoholic hydroxyl group, which is suitable for, but not limited to, the materials for solar energy and semiconductor of the present invention.
  • an alkoxysilane (1), an alkoxysilane (2), an organic solvent (3), water (4), and an acid catalyst (5) can be used.
  • Monitoring can be performed by gel permeation chromatography (GPC) to determine the molecular weight to determine the endpoint of the reaction.
  • GPC gel permeation chromatography
  • a material for solar energy and semiconductor of the present invention prepared using the same contains a dopant component (A), a polymer binder (B), a polysiloxane, and a solvent (C).
  • the alkoxysilane (1) may be one or more, but it must contain an alcoholic hydroxyl group in its molecular structure, or a functional group (6) which can be completely hydrolyzed to form an alcoholic hydroxyl group after the reaction.
  • the functional group (6) include an ester functional group, a propylene oxide functional group, a butylene oxide functional group, and an easily hydrolyzable ether functional group.
  • alkoxysilane (1) examples include 3-glycidyloxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexane)ethyltrimethoxysilane, and 3-glycidyltrimethyl.
  • the alkoxysilane (2) may be one or more, but the molecular structure thereof does not contain the functional group (6) in the above alkoxysilane (1).
  • alkoxysilane (2) examples include phenyltrimethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, vinyltrimethoxysilane, and methylphenyldimethoxysilane. Methyldimethoxysilane, diphenyldimethoxysilane, cyclohexylmethyldimethoxysilane, and the like.
  • the organic solvent (3) is an organic solvent which is not easily hydrolyzed under a strong acid condition of less than 110 ° C and has a solubility in 100 g of water at room temperature of more than 30 g and a boiling point of higher than 110 ° C.
  • Examples of the organic solvent (3) include 1-methoxy-2-propanol, diacetone alcohol, 2-propanol, n-butanol, 3-methoxy-3-methylbutanol, and diethylene glycol.
  • examples of the materials include tap water, deionized water, and ultrapure water.
  • the acid catalyst (5) is used as a catalyst for the hydrolysis reaction of the alkoxysilane (1) and the alkoxysilane (2), and includes the polymerization of the alkoxysilane (1) and the alkoxysilane (2) hydrolyzate.
  • the catalysis of the hydrolysis of the functional group (5) which can be completely hydrolyzed to form an alcoholic hydroxyl group in the substituent of the base type.
  • Examples of the acid catalyst (5) include hydrochloric acid, sulfuric acid, and phosphoric acid (note: phosphoric acid is generally not used when preparing a p-type doping paste), nitric acid, super acid, and the like.
  • GPC Gel permeation chromatography
  • the test conditions were as follows: mobile phase tetrahydrofuran, flow rate 0.2 ml/min, column temperature 40 ° C, and single sample run time 30 minutes.
  • the standard sample used to make the standard curve is polystyrene.
  • the dopant component (A) is a compound widely used in the manufacture of semiconductors (including solar cells).
  • the dopant component (A) is an n-type dopant component containing a compound containing a Group 15 element (also referred to herein as a "Group 15 compound"), or a compound containing a Group 13 element (in this context) Also referred to simply as the "Group 13 compound”) p-type dopant component.
  • Examples of the Group 13 compound contained in the P-type dopant component include B(OH) 3 , B 2 O 3 , and Al 2 O 3 , and one or more kinds of the dopant component (A) are contained.
  • These compounds can form a p-type or high-concentration p-type impurity diffusion layer in a semiconductor substrate, and the diffusion layer itself can also serve as a mask material to block contamination of other impurities.
  • the Group 15 compound contained in the n-type dopant component include H 3 PO 4 , P 2 O 5 , and Bi 2 O 3 , and one or more of these are contained in the dopant component (A).
  • the compound may form an N-type or high-concentration N-type impurity diffusion layer in the semiconductor substrate, and the diffusion layer itself may also serve as a mask material to block contamination of other impurities.
  • the polymer binder (B) has a function of uniformly distributing the above dopant components in the solid component formed after the doping paste and the mask material are dried, thereby contributing to the doping of the target semiconductor substrate. Evenly.
  • the polymer binder (B) is a polyacrylic non-silicon polymer or a non-silicon polymer having a repeating unit containing an alcoholic hydroxyl group.
  • a non-silicon polymer containing an alcoholic hydroxyl group in the repeating unit such as polyvinyl alcohol or polypropylene alcohol, is preferable.
  • the polysiloxane is a siloxane having an alcoholic hydroxyl group in the molecular repeating unit provided by the present invention.
  • the silicon oxide formed by the silicon atom in the oxidative decomposition of the polymer can play a good barrier function to prevent contamination of the coated surface of other materials by the other elements, and can also reduce the doping contained in the material of the present invention.
  • the agent component diffuses outward, thereby reducing external contamination and enhancing doping performance by combining dopant components.
  • the alcoholic hydroxyl group contained therein can also assist the polymer binder (B) to make the distribution of the dopant component more uniform, and at the same time improve the solubility of the polysiloxane in the water-soluble doping paste and the mask material. Thereby, the dopant component and the addition amount of the polysiloxane can be adjusted in a larger range according to actual requirements without affecting the distribution uniformity and stability of the dopant component.
  • the solvent (C) may be a single organic solvent in which no water is added, a mixed solvent of an organic solvent, or a mixed solvent of an organic solvent and water.
  • a single solvent it is preferred that the boiling point is higher than 100 ° C.
  • the solvent is used to prevent the solvent from volatilizing and affecting the quality of the film.
  • a mixed solvent an organic solvent having a boiling point of less than 100 ° C may be used. If an organic solvent having a boiling point of less than 100 ° C is used, it is necessary to have a boiling point of more than 40% by mass or more relative to the total mass of the solvent. a mixed solvent of organic solvent and water. In order to prevent the solvent from volatilizing too quickly to affect the performance in the coating process, a solvent having a boiling point higher than 100 ° C is also preferable even in a mixed solvent.
  • the organic solvent contained in the solvent (C) may, for example, be 1-methoxy-2-propanol, diacetone alcohol, 2-propanol, n-butanol, 3-methoxy-3-methylbutanol, or the like.
  • the method for producing a semiconductor unit of the present invention may be a method of manufacturing a semiconductor unit using a plurality of semiconductor substrates, and the method includes the following steps a to c.
  • Step a applying a first conductivity type impurity diffusion composition on one surface of each semiconductor substrate to form a first conductivity type impurity diffusion composition film
  • Step b heating the semiconductor substrate on which the first conductivity type impurity diffusion composition film is formed, and diffusing the first conductivity type impurity into the semiconductor substrate to form a first conductivity type impurity diffusion layer.
  • Step c heating the semiconductor substrate in an atmosphere containing a gas of the second conductivity type impurity, and diffusing the second conductivity type impurity into the semiconductor substrate to form a second conductivity type impurity diffusion layer.
  • the surfaces of the two-layered semiconductor substrates on which the first conductivity-type impurity-diffusing composition film is formed face each other.
  • a first conductivity type impurity diffusion composition is coated on one surface of the semiconductor substrate 1.
  • the first conductivity type impurity diffusion composition film 2 is formed.
  • the coating method of the first conductive type impurity-diffusing composition is not particularly limited, and a well-known coating method suitable for a semiconductor substrate can be used.
  • a printing method such as screen printing, gravure printing, a spin coating method, a plate brush coating method, a spray method, a doctor blade method, a roll coating method, or an inkjet printing method can be used.
  • the first conductive type impurity-diffusion composition is applied to the entire surface of one surface of the semiconductor substrate 1.
  • a drying step of removing at least a part of the solvent in the first conductive type impurity-diffused composition film 2 may be provided.
  • the drying step for example, heating to 100 degrees Celsius to 300 degrees Celsius is performed to volatilize at least a part of the solvent.
  • the semiconductor substrate 1 is not particularly limited, and examples thereof include n-type single crystal silicon having an impurity concentration of 10 15 to 10 16 atoms/cm 3 , polycrystalline silicon, and a crystalline silicon substrate in which other elements such as ruthenium and carbon are mixed. Further, a p-type crystalline silicon or a semiconductor other than silicon can also be used.
  • the thickness of the semiconductor substrate 1 is 50 to 300 ⁇ m, and the outer shape is preferably a square having one side of 100 to 250 mm. Further, in order to remove the slice damage and the natural oxide film, it is preferably subjected to a surface etching treatment with a hydrofluoric acid solution, an alkali solution or the like.
  • a fine uneven structure called a pile structure on both surfaces.
  • the suede structure is formed, for example, by immersing a silicon substrate in a solution containing 80 degrees Celsius of potassium hydroxide and isopropyl alcohol.
  • the first conductivity type impurity diffusion composition is not particularly limited, and the doping paste and the mask material provided by the present invention are preferred.
  • the semiconductor substrate 3 on which the first conductivity type impurity diffusion composition film 2 is formed on one surface is provided in a two-piece form, and the surface of each of the first conductivity type impurity diffusion composition film 2 is formed.
  • the direction is set in the diffusion boat 4.
  • the diffusion boat 4 is provided with a recess for providing a semiconductor substrate.
  • the groove size and pitch of the diffusion boat are not particularly limited. It is also possible that the diffusion boat is inclined with respect to the horizontal direction.
  • the material of the diffusion boat is not particularly limited as long as it can withstand diffusion temperature, but quartz is preferred.
  • the diffusion boat 4 provided with the semiconductor substrate 3 is heated in the diffusion furnace 16 to diffuse the first conductivity type impurities into the semiconductor substrate 1, thereby forming the first conductivity type impurity diffusion layer 5.
  • the two-piece semiconductor substrate is disposed as described above, even if impurities are diffused from the impurity-diffusing composition film 2 into the gas, it is difficult to reach the surface of the first-conductivity-type impurity-diffusion composition film 2 of the semiconductor substrate. The opposite.
  • the heat treatment temperature and time when the first conductivity type impurity diffusion layer 5 is formed can be appropriately set depending on the impurity diffusion concentration, the diffusion depth, and the like, and the desired diffusion characteristics can be obtained. For example, it can be set to be heated at a temperature of 800 degrees Celsius or more and 1200 degrees Celsius or less for 1 to 120 minutes.
  • the gas atmosphere for heat treatment for forming the first conductive type impurity diffusion layer 5 is not particularly limited, but a mixed atmosphere of nitrogen, oxygen, argon, helium, neon, xenon, xenon, or the like is preferable, and nitrogen gas is further preferable.
  • a mixed atmosphere of oxygen particularly a mixed atmosphere of nitrogen and oxygen having an oxygen content of 5% or less by volume. In order to suppress out-diffusion, it is preferred to carry out impurity diffusion of the first conductivity type in an atmosphere in which oxygen is present in a mixed atmosphere.
  • the distance W1 between the faces formed by the first conductive type impurity-diffused composition film 2 of the two-piece semiconductor substrate is not particularly limited, but is preferably 5 mm or less, and more preferably 1 mm or less.
  • a two-piece semi-guide can be placed in one groove of the diffusion boat 4.
  • the distance W1 between the faces of the first conductivity type impurity-diffusion composition film 2 of the two-piece semiconductor substrate is a short distance.
  • the distance W1 between the faces formed by the first conductivity type impurity-diffusing composition film 2 is 0 mm, that is, the interval is substantially 0 mm (substantially contact).
  • the distance W2 between the opposite faces of the first conductivity type impurity-diffusing composition film forming surface between the two adjacent groups of the semiconductor substrate is not particularly limited, but is preferably 1 to 5 mm, and more preferably 1 to 3 mm.
  • the distance between the faces formed by the first conductivity type impurity diffusion composition film in each group is W1
  • the adjacent two groups are The distance between the reverse faces of the film formation faces of the first conductivity type impurity diffusion composition
  • W1 and W2 satisfy W1 ⁇ W2.
  • the semiconductor substrate 3 on which the first conductivity type impurity diffusion composition film is formed on one side is subjected to heat treatment at a heat treatment temperature lower than that at the time of diffusion and in an atmosphere containing oxygen.
  • At least a part of organic components such as a binder resin in the first conductivity type impurity-diffusing composition film 2 is removed.
  • the concentration of the impurity component in the first conductivity-type impurity-diffusion composition film on the semiconductor substrate can be increased.
  • the diffusibility of the impurity of the first conductivity type is also easily improved.
  • the gas atmosphere in the step b is not particularly limited, but a mixed atmosphere of nitrogen, oxygen, argon, helium, neon, xenon, xenon or the like is preferable, and a mixed atmosphere containing oxygen is more preferable. It is preferably carried out in an atmosphere containing oxygen, so that thermal decomposition of an organic component such as a binder in the film of the first conductivity type impurity-diffusing composition is easier.
  • the content of oxygen in the gas atmosphere is not particularly limited, but is preferably 20% by volume or less. More preferably, the volume content is 5% or less.
  • the arrangement of the semiconductor substrate on the diffusion boat in the step c is the same as that described in the step b. That is, the faces of the two first-piece semiconductor substrates on which the respective first conductivity-type impurity-diffusing composition films are formed are opposed to each other.
  • the distance W1 between the surfaces of the first conductivity type impurity-diffusing composition film 2 of the two-piece semiconductor substrate is not particularly limited, but is preferably 5 mm or less, and more preferably 1 mm or less.
  • a two-piece semiconductor substrate may be disposed in one groove of the diffusion boat 4, and in order to suppress the tendency of outward diffusion, it is preferable that each of the first conductivity type of the two-piece semiconductor substrate
  • the distance W1 between the faces formed by the impurity-diffusing composition film 2 is a short distance. Further preferably, the distance W1 between the faces formed by the impurity-diffusing composition film 2 of the first conductivity type is 0 mm, that is, the interval is substantially 0 mm (substantially contact).
  • the distance W2 between the opposite surfaces of the first diffusion-type impurity-diffusing composition film formation surface between adjacent groups of the semiconductor substrate is not particularly limited, but is preferably 1 to 5 mm, and more preferably 1 to 3 mm.
  • the distance between the faces formed by the first conductivity type impurity diffusion composition film in each group is W1
  • the adjacent two groups are The distance between the reverse faces of the film formation faces of the first conductivity type impurity diffusion composition
  • W1 and W2 satisfy W1 ⁇ W2.
  • the semiconductor substrate is heated while flowing into the gas containing the second conductivity type impurity to form the second conductivity type impurity diffusion layer.
  • the gas containing the second conductivity type impurity in the case of an n-type, it may be a POCl 3 gas, and in the case of a p-type, a gas such as BBr 3 or BCl 3 may be mentioned.
  • POCl 3 gas is bubbled through to give a mixed gas of nitrogen or nitrogen / oxygen to the POCl 3 solution, or solution of POCl 3 may be heated.
  • the heating temperature is preferably 750 degrees Celsius to 1050 degrees Celsius, and further preferably 800 degrees Celsius to 1000 degrees Celsius.
  • the gas atmosphere is not particularly limited, but a mixed atmosphere of nitrogen, oxygen, argon, helium, neon, xenon, xenon or the like is preferable, and a mixed atmosphere of nitrogen and oxygen is more preferable, and a volume fraction of oxygen is particularly preferably 5% or less.
  • a mixed atmosphere of nitrogen and oxygen is not particularly limited, but a mixed atmosphere of nitrogen, oxygen, argon, helium, neon, xenon, xenon or the like is preferable, and a mixed atmosphere of nitrogen and oxygen is more preferable, and a volume fraction of oxygen is particularly preferably 5% or less.
  • the process time for changing the gas atmosphere can be shortened, it is preferable to carry out the c process without changing the atmosphere of the b process.
  • the ratio of nitrogen gas to oxygen gas in the gas atmosphere in the step b is the same as the ratio of nitrogen gas and oxygen gas in the gas atmosphere in the step c.
  • the heat-treated material layer 6 of the first-conductivity-type impurity-diffusion composition film remains on the upper surface of the first-conductivity-type impurity diffusion layer 5.
  • This is preferably performed as a mask for the impurity containing the second conductivity type impurity. In doing so, it is possible to suppress the second conductivity type impurity from being mixed into the impurity diffusion layer 5 of the first conductivity type.
  • the c step is performed after the step b.
  • the step c process it is preferable to perform the c process continuously in the b process after the b process.
  • the step c it is referred to as the step c after the step b and the step c is continued.
  • the heating temperature in forming the second conductivity type impurity diffusion layer in the step c is preferably 50 to 200 degrees Celsius lower than the heating temperature when the first conductivity type impurity diffusion layer is formed in the step b described above. Pass The heating temperature when the second conductivity type impurity diffusion layer is formed in the step c is lower than the heating temperature when the first conductivity type impurity diffusion layer is formed in the step b by 50 to 200 degrees Celsius, and after the step b, the step b is continued. When the step c is performed, the influence on the heating of the first conductive type impurity diffusion layer formed in the step b can be minimized, and the diffusion of the first conductivity type impurity can be easily controlled.
  • the first conductivity type is preferably p-type, and the second conductivity type is preferable. It is n type.
  • the method for producing a semiconductor unit of the present invention preferably includes the step of d described below.
  • a step of oxidizing the surface of the semiconductor substrate in an oxygen atmosphere is a step of oxidizing the surface of the semiconductor substrate in an oxygen atmosphere.
  • the time required for the step d is not particularly limited, and it is preferable that the step d can be performed after the step b or after the step c.
  • the step d is performed continuously in the step c. In doing so, it is possible to remove the diffusion layer (contamination layer) which is generated by outward diffusion at a position where diffusion does not originally occur.
  • the diffusion layer contamination layer
  • the atmosphere may contain oxygen, and the atmosphere is not particularly limited, and a mixed atmosphere of nitrogen, argon, helium, neon, xenon, xenon, and the like with oxygen may be used.
  • a mixed atmosphere of nitrogen and oxygen is preferable, and a mixed atmosphere of nitrogen and oxygen having an oxygen volume content of 20% or more is further preferable, and a pure oxygen atmosphere is particularly preferable. The more oxygen content, the higher the oxidation rate.
  • semiconductor devices can be fabricated using known methods. These methods are not particularly limited, and for example, the following methods can be cited as an example.
  • An antireflection layer or a passivation layer is formed on both surfaces of the semiconductor substrate.
  • These layers can use various known materials. These layer single layers may also be multi-layered or may be used. For example, a silicon oxide layer can be used, The aluminum oxide layer, the SiNx layer, and the amorphous silicon layer are laminated. These layers can be formed by a vapor deposition method such as a plasma CVD method, an ALD (atomic layer deposition) method, or a coating method.
  • a layer which functions as both an antireflection layer and a passivation layer As such a layer, a nitride layer formed by a plasma CVD method can be cited.
  • a surface protective layer containing silicon oxide, aluminum oxide, or the like may be present between the antireflection layer and the semiconductor substrate. Moreover, it is possible to partially change the composition of the antireflection layer.
  • the antireflection layer is formed on the entire surface or a part of the light receiving surface and the inner surface. It is also possible to provide a contact hole on the antireflection layer on the upper surface of the impurity diffusion layer. In doing so, the subsequently formed electrode and the impurity diffusion layer can form an electrical contact.
  • the method of forming the contact holes is not limited, but etching is preferred. In the etching, a suitable substance may be used as the material of the antireflection layer, and examples thereof include ammonium fluoride and the like.
  • the burn-through method can also be used in appropriate cases.
  • the burn-through method is a method in which an electrode is formed on the antireflection layer, and the glass particles are melted by a firing process, and the electrode and the semiconductor substrate are bonded together while the reflection preventing layer is decomposed, and the method is formed by firing, that is, burning through. law.
  • the material suitable for the antireflection layer is silicon nitride.
  • electrodes are formed on both surfaces of the semiconductor substrate. It is not particularly limited, and a method generally used in the formation of an electrode can be used.
  • a metal paste for a surface electrode containing metal particles and glass particles can be used.
  • the metal paste for the surface electrode may be applied to form a desired pattern on the field in which the impurity diffusion layer is formed, and the metal particles may be passed through the reflection preventing layer or the passivation layer by heat treatment, thereby forming an electrode on the impurity diffusion layer.
  • a surface electrode is formed.
  • the metal paste for the surface electrode for example, silver paste or the like which is commonly used in the art can be used.
  • FIG. 5 the double-sided light receiving type solar battery cell according to the embodiment will be schematically illustrated.
  • a process diagram of an example of a manufacturing method is shown in a sectional view.
  • the invention is not limited by the process diagram.
  • the semiconductor substrate is an n-type semiconductor substrate
  • the first conductivity type is a p-type
  • the second conductivity type is an n-type
  • an n-type semiconductor substrate 7 having a thickness of about 50 ⁇ m to 300 ⁇ m is prepared as shown in Fig. 5i.
  • the n-type semiconductor substrate 7 is formed by slicing a single crystal or a polycrystalline silicon ingot formed using a CZ (Czochrzlski) method, an FZ (Floating Zone) method, an EFG (Edge Difined Film Growth) method, a casting method, or the like.
  • a CZ Czochrzlski
  • FZ Floating Zone
  • EFG Edge Difined Film Growth
  • a casting method or the like.
  • it has an n-type impurity (phosphorus or the like) having a concentration of 1*10 15 atoms/cm 3 to 1*10 19 atoms/cm 3 .
  • the n-type semiconductor substrate 7 is washed with an aqueous alkali solution.
  • an aqueous alkali solution organic substances, particles, and the like existing on the surface of the n-type semiconductor substrate 7 can be removed, and the effect of passivation can be improved.
  • a general well-known RCA cleaning method or the like can be exemplified.
  • the n-type semiconductor substrate 7 is immersed in a mixed solution of ammonia water-hydrogen peroxide, and treated at 60 degrees Celsius to 80 degrees Celsius to remove organic matter and particles.
  • the washing time is preferably from 10 seconds to 10 minutes, more preferably from 30 seconds to 5 minutes.
  • the n-type semiconductor substrate 7 is preferably a pile structure (not shown) having a pyramid structure on both surfaces by a method such as alkali etching. Thereby, the reflection of sunlight can be suppressed.
  • a p-type impurity diffusion composition is applied on one surface to form a p-type impurity diffusion composition film 8.
  • the semiconductor substrates 7 are placed together in the diffusion boat 4 in such a manner that the faces formed by the respective impurity diffusion composition films are opposed to each other.
  • the p-type impurity-diffusing composition film 8 is formed into a heat-treated product 10 by heat treatment for the purpose of heat diffusion.
  • heat treatment temperature preferably 800 Celsius ⁇ 1200 degrees Celsius.
  • the n-type semiconductor substrate 7 is heated to 750 degrees Celsius to 950 degrees Celsius, and the phosphosilicate glass layer 11 and the n-type are simultaneously introduced into the POCl 3 solution by bubbling nitrogen or a mixed atmosphere of nitrogen and oxygen.
  • the impurity diffusion layer 12 is simultaneously formed.
  • the heat-treated product 10 of the p-type impurity-diffusion composition film can suppress the diffusion of phosphorus into the inner surface of the p-type impurity diffusion layer 9.
  • the semiconductor substrate is subjected to an oxidation process in an atmosphere containing oxygen to oxidize the phosphorus contaminated layer.
  • the heat-treated material 10 of the oxidized contaminated layer p-type impurity diffusion composition film and the phosphosilicate glass layer 11 are integrated (not shown).
  • the heat-treated product 10 of the p-type impurity diffusion composition film and the phosphosilicate glass 11 are removed.
  • a method of removal for example, it is immersed in an etching liquid such as hydrofluoric acid.
  • an antireflection layer and a passivation layer 13 are formed on the light receiving surface and the inner surface, respectively.
  • the antireflection layer and passivation layer 13 as described above, a preferred example of a silicon nitride layer, a titanium oxide layer, a silicon oxide layer or an aluminum oxide layer can be mentioned.
  • the antireflection layer and the passivation layer 13 are formed on a part of the light receiving surface and the inner surface.
  • the p-electrode 14 and the n-electrode 15 are formed on the respective upper surfaces of the light-receiving surface and the inner surface in a portion where the anti-reflection layer and the passivation layer 13 are not present.
  • the electrode can be formed by imparting a slurry capable of forming an electrode and then performing heat treatment.
  • FIG. 5 a method in which a missing portion is provided in advance on the anti-reflection layer and passivation layer 13 on the n-type semiconductor substrate, and the p-electrode 14 and the n-electrode 15 are formed thereon are exemplified.
  • a slurry containing the glass-penetrating glass particles is used as the slurry for electrode formation, and the antireflection layer and the passivation layer 13 are formed after the firing. An ohmic contact of the impurity diffusion layer and the electrode can be achieved. As described above, a solar unit can be obtained.
  • Materials for solar energy and semiconductors of the present invention include, but are not limited to, dopant pastes and mask materials.
  • the doping paste and the mask material prepared according to Examples 1 to 26 and Comparative Examples 1 to 3 were respectively coated on a 6-inch N-type single crystal silicon wafer using spin coating conditions, and then subjected to thermal diffusion to evaluate the correlation. performance.
  • the spin coating conditions were: (A) 1000 rpm for 10 seconds, (B) 1500 rpm for 10 seconds, and (C) 2000 rpm for 10 seconds.
  • Wafer A Single-sided polishing of semiconductor, CZ Czochralski doped N-type single crystal silicon wafer, crystal orientation 100, resistivity 0.5-6 ⁇ cm, thickness 625 ⁇ m.
  • Wafer B Double-sided fleece for solar cells, CZ Czochralski doped N-type single crystal silicon wafer, crystal orientation 100, resistivity 1-7 ⁇ .cm, thickness 180 microns.
  • the placement of the silicon wafer is as shown in Fig. 1 of the specification, and the placement of the silicon wafer in the evaluation of diffusivity in the gas is as shown in Fig. 2 of the specification.
  • Resistance tester Japan NAPSON four-probe resistivity tester, manual version RT-70V/RG-7. The performance evaluation results are as follows:
  • a p-type impurity diffusion composition was applied to the entire surface by a spin coater, and dried at 150 ° C for 1 minute to form a surface.
  • a semiconductor substrate of a p-type impurity diffusion composition film was applied to the entire surface by a spin coater, and dried at 150 ° C for 1 minute to form a surface.
  • a semiconductor substrate having a p-type impurity diffusion composition film formed on one surface thereof is provided in the diffusion boat.
  • the distance between the faces of the two-piece semiconductor substrate on which the p-type impurity diffusion composition film is formed and the distance between the faces on which the p-type impurity diffusion composition film is not formed are each It is 3mm.
  • the diffusion boat was introduced into a diffusion furnace (Opyang Heat Treatment Co., Ltd., 206A-M100) having an O 2 : 0.2 L/min and N 2 : 9.8 L/min, and set to 700 ° C. Thereafter, the temperature was raised to 950 degrees Celsius at a rate of 15 degrees Celsius/min, and heat treatment was performed at 950 degrees Celsius for 30 minutes to form a p-type impurity diffusion layer.
  • a diffusion furnace Opyang Heat Treatment Co., Ltd., 206A-M100
  • the temperature was lowered to 830 degrees Celsius at a rate of 10 degrees Celsius/min.
  • O 2 : 0.2 L/min, N 2 : 9.8 L/min, and N 2 : 1.5 L/min after bubbling in POCl 3 were flowed into the diffusion furnace for 5 minutes. Thereafter, the nitrogen flow bubbling in the POCl 3 was stopped, and heat treatment was carried out for 12 minutes at the same temperature in an inflow gas of O 2 : 0.2 L/min and N 2 : 9.8 L/min to form a p-type impurity diffusion composition. An n-type impurity diffusion layer is formed at a position outside the field of the film. Thereafter, the temperature was lowered to 700 degrees Celsius at a rate of 10 degrees Celsius/min, and the n-type semiconductor substrate was taken out from the diffusion furnace.
  • the glass layer remaining on the surface of the n-type semiconductor substrate (the human processed material 10 of the p-type impurity diffusion composition and the phosphosilicate glass layer 11) is removed using hydrofluoric acid.
  • the average value of the sheet resistance in the field of the P-type impurity diffusion layer was 65 ⁇ / ⁇ , and the average value of the sheet resistance of the n-type impurity diffusion layer region formed on the reverse surface of the surface formed by the p-type impurity diffusion composition film was 55 ⁇ / ⁇ .
  • the boron element concentration of the surface layer of the n-type semiconductor substrate was measured by SIMS (Secondary Ion Mass Spectrometer, Cameca, IMS-7F). One ion uses Cs+.
  • the boron concentration in the surface layer of the N-type semiconductor substrate is 7*10 17 atoms/cm 3 or less, and boron contamination on the surface layer of the n-type semiconductor substrate is suppressed.
  • Example 18 On one surface of the n-type semiconductor substrate on which the texturing was performed on both surfaces, the same p-type impurity diffusion composition as in Example 18 was applied over the entire surface by spin coating, at 150 ° C. After drying for 1 minute, a semiconductor substrate on which a p-type impurity diffusion composition film was formed was formed.
  • a semiconductor substrate on which a p-type impurity diffusion composition film is formed on one side is provided in the diffusion boat.
  • the distance between the surfaces of the two-piece semiconductor substrate on which the p-type impurity diffusion composition film was formed was 0 mm, and the distance between the surfaces on which the p-type impurity diffusion composition film was not formed was 3 mm.
  • a diffusion boat was introduced while being set to 700 ° C. Thereafter, the temperature was raised to 950 degrees Celsius at a rate of 15 degrees Celsius/min, and heat treatment was performed at 950 degrees Celsius for 30 minutes to form a p-type impurity diffusion layer.
  • the temperature was lowered to 830 degrees Celsius at a rate of 10 degrees Celsius/min.
  • O 2 : 0.2 L/min, N 2 : 9.8 L/min, and N 2 : 1.5 L/min after bubbling in POCl 3 were flowed into the diffusion furnace for 5 minutes. Thereafter, the nitrogen flow bubbling in the POCl 3 was stopped, and heat treatment was carried out for 12 minutes at the same temperature in an inflow gas of O 2 : 0.2 L/min and N 2 : 9.8 L/min to form a p-type impurity diffusion composition. An n-type impurity diffusion layer is formed at a position outside the region of the film. Thereafter, the temperature was lowered to 700 degrees Celsius at a rate of 10 degrees Celsius/min, and the n-type semiconductor substrate was taken out from the diffusion furnace.
  • the glass layer remaining on the surface of the n-type semiconductor substrate (the human processed material 10 of the p-type impurity diffusion composition and the phosphosilicate glass layer 11) is removed using hydrofluoric acid.
  • the average value of the sheet resistance of the P-type impurity diffusion layer region was 67 ⁇ / ⁇
  • the average value of the sheet resistance of the n-type impurity diffusion layer region formed on the reverse surface of the surface formed by the p-type impurity diffusion composition film was 56 ⁇ / ⁇ .
  • the boron element concentration of the surface layer of the n-type semiconductor substrate was measured by SIMS (Secondary Ion Mass Spectrometer, Cameca, IMS-7F). One ion uses Cs+.
  • the boron concentration in the surface layer of the N-type semiconductor substrate is 6*10 16 atoms/cm 3 or less, and boron contamination on the surface layer of the n-type semiconductor substrate is suppressed.
  • Example 18 On one surface of the n-type semiconductor substrate on which the texturing was performed on both surfaces, the same p-type impurity-diffusing composition as in Example 18 was applied to the entire surface by spin coating, and dried at 150 ° C for 1 minute to prepare A semiconductor substrate on which a p-type impurity diffusion composition film is formed on one side.
  • a semiconductor substrate on which a p-type impurity diffusion composition film is formed on one side is provided in the diffusion boat.
  • the distance between the surfaces of the two-piece semiconductor substrate on which the p-type impurity diffusion composition film was formed was 0 mm, and the distance between the surfaces on which the p-type impurity diffusion composition film was not formed was 3 mm.
  • the diffusion boat was introduced into a diffusion furnace (Opyang Heat Treatment Co., Ltd., 206A-M100) having an O 2 : 0.2 L/min and N 2 : 9.8 L/min, and set to 700 ° C. Thereafter, the temperature was raised to 950 degrees Celsius at a rate of 15 degrees Celsius/min, and heat treatment was performed at 950 degrees Celsius for 30 minutes to form a p-type impurity diffusion layer.
  • a diffusion furnace Opyang Heat Treatment Co., Ltd., 206A-M100
  • the temperature was lowered to 830 degrees Celsius at a rate of 10 degrees Celsius/min.
  • O 2 : 0.2 L/min, N 2 : 9.8 L/min, and N 2 : 1.5 L/min after bubbling in POCl 3 were flowed into the diffusion furnace for 5 minutes. Thereafter, the nitrogen flow bubbling in the POCl 3 was stopped, and heat treatment was carried out for 12 minutes at the same temperature in an inflow gas of O 2 : 0.2 L/min and N 2 : 9.8 L/min to form a p-type impurity diffusion composition. An n-type impurity diffusion layer is formed at a position outside the region of the film. Thereafter, the temperature was lowered to 700 degrees Celsius at a rate of 10 degrees Celsius/min, and the n-type semiconductor substrate was taken out from the diffusion furnace.
  • the temperature was raised to 900 degrees Celsius at a rate of 10 degrees Celsius/min, and the surface of the semiconductor substrate was oxidized by heat treatment at a temperature of 900 ° C and O 2 : 5 L/min for 20 minutes at the same temperature.
  • the temperature was lowered to 700 degrees Celsius at a rate of 10 degrees Celsius/min, and the n-type semiconductor substrate was taken out from the diffusion furnace.
  • the glass layer remaining on the surface of the n-type semiconductor substrate (the human processed material 10 of the p-type impurity diffusion composition and the phosphosilicate glass layer 11) is removed using hydrofluoric acid.
  • P-type impurity diffusion layer region The average value of the sheet resistance was 60 ⁇ / ⁇ , and the average value of the sheet resistance of the n-type impurity diffusion layer region formed on the reverse surface of the surface formed by the p-type impurity diffusion composition film was 51 ⁇ / ⁇ .
  • the boron element concentration of the surface layer of the n-type semiconductor substrate was measured by SIMS (Secondary Ion Mass Spectrometer, Cameca, IMS-7F). One ion uses Cs+.
  • the boron concentration in the surface layer of the N-type semiconductor substrate is 5*10 15 atoms/cm 3 or less, and boron contamination on the surface layer of the n-type semiconductor substrate is suppressed.
  • Example 18 On one surface of the n-type semiconductor substrate on which the texturing was performed on both surfaces, the same p-type impurity-diffusing composition as in Example 18 was applied to the entire surface by spin coating, and dried at 150 ° C for 1 minute to prepare A semiconductor substrate on which a p-type impurity diffusion composition film is formed on one side.
  • a semiconductor substrate on which a p-type impurity diffusion composition film is formed on one side is provided in the diffusion boat.
  • the distance between the surfaces of the two-piece semiconductor substrate on which the p-type impurity diffusion composition film was formed was 0 mm, and the distance between the surfaces on which the p-type impurity diffusion composition film was not formed was 3 mm.
  • the diffusion boat was introduced into a diffusion furnace (Opyang Heat Treatment Co., Ltd., 206A-M100) having an O2: 0.2 L/min and N2: 9.8 L/min, and set to 700 degrees Celsius. Thereafter, the temperature was raised to 950 degrees Celsius at a rate of 15 degrees Celsius/min, and heat treatment was performed at 950 degrees Celsius for 30 minutes to form a p-type impurity diffusion layer.
  • a diffusion furnace Opyang Heat Treatment Co., Ltd., 206A-M100
  • the temperature was lowered to 830 degrees Celsius at a rate of 10 degrees Celsius/min.
  • O 2 : 0.2 L/min, N 2 : 9.8 L/min, and N2: 1.5 L/min after bubbling in POCl 3 were flowed into the diffusion furnace for 5 minutes. Thereafter, the nitrogen flow bubbling in POCl 3 was stopped, and heat treatment was carried out for 12 minutes at the same temperature in an inflow gas of O 2 : 0.2 L/min and N 2 : 9.8 L/min to form a p-type impurity diffusion composition film. An n-type impurity diffusion layer is formed at a position outside the region. Thereafter, the temperature was lowered to 700 degrees Celsius at a rate of 10 degrees Celsius/min, and the n-type semiconductor substrate was taken out from the diffusion furnace.
  • the glass layer remaining on the surface of the n-type semiconductor substrate (the human processed material 10 of the p-type impurity diffusion composition and the phosphosilicate glass layer 11) is removed using hydrofluoric acid.
  • the average value of the sheet resistance of the p-type impurity diffusion layer region was 62 ⁇ / ⁇
  • the average value of the sheet resistance of the n-type impurity diffusion layer region formed on the reverse surface of the surface formed by the p-type impurity diffusion composition film was 61 ⁇ / ⁇ .
  • the boron element concentration of the surface layer of the n-type semiconductor substrate was measured by SIMS (Secondary Ion Mass Spectrometer, Cameca, IMS-7F). One ion uses Cs+.
  • the boron concentration in the surface layer of the N-type semiconductor substrate is 2*10 16 atoms/cm 3 or less, and boron contamination on the surface layer of the n-type semiconductor substrate is suppressed.
  • Example 18 On one surface of the n-type semiconductor substrate on which the texturing was performed on both surfaces, the same p-type impurity-diffusing composition as in Example 18 was applied to the entire surface by spin coating, and dried at 150 ° C for 1 minute to prepare A semiconductor substrate on which a p-type impurity diffusion composition film is formed on one side.
  • a semiconductor substrate on which a p-type impurity diffusion composition film is formed on one side is provided in the diffusion boat.
  • the distance between the surfaces of the two-piece semiconductor substrate on which the p-type impurity diffusion composition film was formed was 0 mm, and the distance between the surfaces on which the p-type impurity diffusion composition film was not formed was 3 mm.
  • the diffusion boat was introduced into a diffusion furnace (Opyang Heat Treatment Co., Ltd., 206A-M100) having an O 2 : 0.2 L/min and N 2 : 9.8 L/min, and set to 700 ° C.
  • a diffusion furnace Opyang Heat Treatment Co., Ltd., 206A-M100
  • the temperature was raised to 900 degrees Celsius at a rate of 15 degrees Celsius/min, and the surface of the semiconductor substrate was oxidized by heat treatment at a temperature of 900 ° C and O 2 : 5 L/min for 20 minutes at the same temperature.
  • the temperature was raised to 950 degrees Celsius at a rate of 15 degrees Celsius/min, and heat treatment was performed at 950 degrees Celsius for 30 minutes to form a p-type impurity diffusion layer.
  • the temperature was lowered to 830 degrees Celsius at a rate of 10 degrees Celsius/min.
  • O 2 : 0.2 L/min, N 2 : 9.8 L/min, and N 2 : 1.5 L/min after bubbling in POCl 3 were flowed into the diffusion furnace for 5 minutes. Thereafter, the nitrogen flow bubbling in the POCl 3 was stopped, and heat treatment was carried out for 12 minutes at the same temperature in an inflow gas of O 2 : 0.2 L/min and N 2 : 9.8 L/min to form a p-type impurity diffusion composition. An n-type impurity diffusion layer is formed at a position outside the region of the film. Thereafter, the temperature was lowered to 700 degrees Celsius at a rate of 10 degrees Celsius/min, and the n-type semiconductor substrate was taken out from the diffusion furnace.
  • the glass layer remaining on the surface of the n-type semiconductor substrate (the heat-treated product 10 of the p-type impurity diffusion composition and the phosphosilicate glass layer 11) is removed using hydrofluoric acid.
  • the average value of the sheet resistance of the p-type impurity diffusion layer region was 64 ⁇ / ⁇
  • the average value of the sheet resistance of the n-type impurity diffusion layer region formed on the reverse surface of the surface formed by the p-type impurity diffusion composition film was 65 ⁇ / ⁇ .
  • the boron element concentration of the surface layer of the n-type semiconductor substrate was measured by SIMS (Secondary Ion Mass Spectrometer, Cameca, IMS-7F). One ion uses Cs+.
  • the boron concentration in the surface layer of the N-type semiconductor substrate is 4*10 16 atoms/cm 3 or less, and boron contamination on the surface layer of the n-type semiconductor substrate is suppressed.
  • Example 18 On one surface of the n-type semiconductor substrate subjected to the texturing process on both surfaces, the same p-type impurity-diffusing composition as in Example 18 was applied to the entire surface by spin coating, and dried at 150 ° C for 1 minute to prepare. A semiconductor substrate on which a p-type impurity diffusion composition film is formed on one surface.
  • the semiconductor substrate on which the p-type impurity diffusion composition film was formed on one surface was provided in the diffusion boat in the direction in which the respective p-type impurity diffusion composition films were formed.
  • the distance of each semiconductor substrate was all 3 mm.
  • the diffusion boat was introduced into a diffusion furnace (Opyang Heat Treatment Co., Ltd., 206A-M100) having an O 2 : 0.2 L/min and N 2 : 9.8 L/min, and set to 700 ° C. Thereafter, the temperature was raised to 950 degrees Celsius at a rate of 15 degrees Celsius/min, and heat treatment was performed at 950 degrees Celsius for 30 minutes to form a p-type impurity diffusion layer.
  • a diffusion furnace Opyang Heat Treatment Co., Ltd., 206A-M100
  • the temperature was lowered to 830 degrees Celsius at a rate of 10 degrees Celsius/min.
  • O 2 : 0.2 L/min, N 2 : 9.8 L/min, and N 2 : 1.5 L/min after bubbling in POCl 3 were flowed into the diffusion furnace for 5 minutes. Thereafter, the nitrogen flow bubbling in the POCl 3 was stopped, and heat treatment was carried out for 12 minutes at the same temperature in an inflow gas of O 2 : 0.2 L/min and N 2 : 9.8 L/min to form a p-type impurity diffusion composition. An n-type impurity diffusion layer is formed at a position outside the region of the film. Thereafter, the temperature was lowered to 700 degrees Celsius at a rate of 10 degrees Celsius/min, and the n-type semiconductor substrate was taken out from the diffusion furnace.
  • the glass layer remaining on the surface of the n-type semiconductor substrate (the human processed material 10 of the p-type impurity diffusion composition and the phosphosilicate glass layer 11) is removed using hydrofluoric acid.
  • the average value of the sheet resistance of the P-type impurity diffusion layer region was 66 ⁇ / ⁇
  • the average value of the sheet resistance of the n-type impurity diffusion layer region formed on the reverse surface of the surface formed by the p-type impurity diffusion composition film was 56 ⁇ / ⁇ .
  • the boron element concentration in the surface layer of the n-type semiconductor substrate was measured by SIMS (Secondary Ion Mass Spectrometer, Cameca, IMS-7F). One ion uses Cs+.
  • the boron concentration in the surface layer of the N-type semiconductor substrate is 1*10 20 atoms/cm 3 or less, and boron contamination occurs on the surface layer of the n-type semiconductor substrate.
  • the semi-conductive method of the present invention is compared with the performance of Comparative Example 4.
  • the method of manufacturing the bulk cell can very effectively suppress the outward diffusion of boron, and in particular, greatly reduce the contamination on the surface of the n-type substrate.
  • the polysiloxanes provided by the present invention can be used in doping pastes, mask materials, semiconductors (including solar cells).

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Abstract

一种聚硅氧烷，含有至少一种选自下式1所示的分子结构片段, 式1中，Q为含有醇羟基且主链碳原子数小于12的烷基、或者含有醇羟基且主链非氢原子数小于12且含杂原子的烷基；T为羟基、烷基、含有醇羟基且主链碳原子数小于12的烷基、或者含有醇羟基且主链非氢原子数小于12且含杂原子的烷基。使用上述聚硅氧烷制备的掺杂浆料以及掩膜材料在具有优良扩散性的基础上，同时还具有优良的阻隔性和极小的气中扩散。并且，根据半导体的制造方法，进一步减少了掺杂浆料中的掺杂杂质的气中扩散，从而可以进一步提升掺杂的工艺品质。

Description

聚硅氧烷、半导体用材料、半导体及太阳能电池制备方法 技术领域
本发明涉及聚硅氧烷、用于太阳能和半导体的材料、半导体单元的制备方法以及太阳能电池。具体涉及一系列聚硅氧烷的有机合成、用于太阳能和半导体的掺杂材料以及掩膜材料、使用此材料的半导体单元的制备方法以及太阳能电池。
背景技术
在以往的半导体或者太阳能电池的制造中，在半导体基板中形成p型或者n型杂质扩散层的情况下，使用气体掺杂剂或者掺杂浆料的方法均被提出过。但是，使用前述现有气体掺杂剂或者掺杂浆料进行高温热扩散时，需要在非扩散面形成阻隔层。从而导致工艺过程冗长、复杂，同时成本也相应提高。如果使用离子注入方法，所需设备成本、维护成本都比较高。而且，现有浆料的性能、成本等难以达到一个有力平衡，导致其在太阳能电池产业中不具市场竞争力(文献[1])。
特别是对于两面都可以受光发电的双面电池的制造工艺中，在太阳能电池所使用的半导体基板中使得p型以及n型的杂质扩散以形成杂质扩散层的工艺中，分别针对p型杂质扩散层以及n型杂质扩散层采用不同的工序。但是这样的方法存在工序数增加的问题。针对这些问题，作为更简便的方法，提出了在半导体基板上赋予含有受主元素的p型杂质扩散组合物，热处理形 成p型杂质扩散层之后，利用p型杂质扩散组合物的热处理物的一部分作为掩膜形成n型杂质扩散层的方法。
另外气体掺杂剂一般为三溴化硼、磷烷、三氯氧磷等剧毒物质，对管路、尾气吸收设备的要求较高，而且一旦泄露有发生大事故的可能、以及对周围环境产生污染。
专利文献[1]：魏青竹、陆俊宇、连维飞、倪志春，N型双面电池及其制作方法：中国，CN201510020649.4[P].2015-01-15.[1]
发明内容
为了解决现有半导体掺杂(包括太阳能电池p型和n型掺杂)中高成本、所使用的掺杂材料高毒性和环境污染性、掺杂的不均匀性而导致的良品率低下的缺陷，本发明提供一种聚硅氧烷、以及使用该聚硅氧烷制备的用于太阳能和半导体的材料、同时也提供了使用该用于太阳能电池和半导体的材料的半导体单元以及太阳能电池的制造工艺。
本发明公开了一种聚硅氧烷，含有至少一种选自下式1所示的分子结构片段，
Figure PCTCN2017098627-appb-000001
式1中，Q为含有醇羟基且主链碳原子数小于12的烷基、或者含有醇羟基且主链非氢原子数小于12且含杂原子的烷基；T为羟基、烷基、含有醇羟基且主链碳原子数小于12的烷基、或者含有醇羟基且主链非氢原子数小于12且含杂原子的烷基。
出于为了增加水中的溶解性、并且还通过与硼发生络合而提高硼分布的 均一性的考虑，所述Q优选为式2所示的结构片段，
Figure PCTCN2017098627-appb-000002
式2中，X为碳原子数小于7的烷基、或者主链非氢原子数小于7且含杂原子的的烷基；R1、R2、R3分别独立为氢原子、碳原子数小于3的取代基，或者R2与X上的碳原子连接成为环状取代基。
出于为了使得聚硅氧烷易于热分解、并且使得硅含量能够使阻隔性和抑制气中扩散的性能达到要求的考虑，所述X优选为主链非氢原子数小于7且含杂原子的烷基。
在本文中使用时，“气中扩散”表示：在扩散过程中，掺杂浆料或者掩膜材料中的扩散剂成分向其周围的气体中挥发，并在气体中扩散。
出于水中溶解性、以及使得确保硅含量能够使阻隔性、抑制气中扩散的性能达到要求的考虑，优选所述R1、R2、R3分别独立为氢原子、碳原子数为1的取代基，或者R2与X上的碳原子连接成为环状取代基。进一步优选地，所述R1、R2、R3分别独立为氢原子。
所述聚硅氧烷优选还含有摩尔含量1～99％的至少一种选自下式3所示的分子结构片段，
Figure PCTCN2017098627-appb-000003
式3中X1为碳原子数小于8的烷基、或碳原子数小于10的芳基；Y1为羟基、碳原子数小于10的芳基、或者碳原子数小于8的烷基。
考虑到除了在有机溶剂中的溶解性之外，还保持一定程度在水中的溶解性，所述式2所示的分子结构片段的摩尔含量优选为1～50％。
出于成本方面的考虑以及利用羟基的亲水性来保持水中溶解度的考虑，所述Y1优选为羟基。
出于为了增加水中的溶解性、并且还通过与硼发生络合而提高硼分布的均一性的考虑，优选T为羟基、碳原子数小于8的烷基，或者含有式4所示的结构，
Figure PCTCN2017098627-appb-000004
式4中Z为碳原子数小于7的烷基、或者主链非氢原子数小于7且含杂原子的的烷基；R1、R2、R3分别独立为氢原子、碳原子数小于3的取代基，或者R5与Z上的碳原子连接成为环状取代基。
出于为了使得聚硅氧烷易于热分解、并且使得硅含量能够使阻隔性和抑制气中扩散的性能达到要求的考虑，所述Z优选为主链非氢原子数小于7且含杂原子的的烷基。
出于为了使得聚硅氧烷中硅含量能够使阻隔性和抑制气中扩散的性能达到要求的考虑，所述T优选为羟基。
由于环氧乙烷与聚合导致保存稳定性降低，优选所述聚硅氧烷不含有环氧乙烷结构。
为了获得良好的水溶性以及有机溶剂溶解性，所述聚硅氧烷优选仅由Q为式2所示的分子结构片段构成的式1所示的分子结构片段组成。
由于单一分子的均匀性更好，所述分子结构片段优选为相同的分子结构片段。
由于分子量过高溶解性总体降低，同时胶体化也容易发生，优选所述聚硅氧烷的重均分子量为500～50000。
出于存放使用中即使分子量增大也不会导致局部不均匀的考虑，优选所述聚硅氧烷的重均分子量为1000～11000。
出于延长保质期的考虑，优选所述聚硅氧烷的重均分子量为1500～5500。
对于本发明的聚硅氧烷没有特别限定，具体可列举如下的例子。重复单元结构的实际排列方式并不限于下述结构例所示。
Figure PCTCN2017098627-appb-000005
Figure PCTCN2017098627-appb-000006
Figure PCTCN2017098627-appb-000007
Figure PCTCN2017098627-appb-000008
Figure PCTCN2017098627-appb-000009
Figure PCTCN2017098627-appb-000010
Figure PCTCN2017098627-appb-000011
Figure PCTCN2017098627-appb-000012
Figure PCTCN2017098627-appb-000013
Figure PCTCN2017098627-appb-000014
Figure PCTCN2017098627-appb-000015
Figure PCTCN2017098627-appb-000016
Figure PCTCN2017098627-appb-000017
本发明还公开了一种用于太阳能和半导体的材料(以下，也简称为“本发明的材料”)，其含有前文所述的聚硅氧烷。
所述的用于太阳能和半导体的材料，还可含有：掺杂剂成分A、高分子粘结剂B和溶剂C。
本发明的用于太阳能和半导体的材料在用作为掩模材料时也可以不含掺杂剂成分A。
对于掺杂剂成分A没有特别的限定，优选所述掺杂剂成分A为包含第5主族元素的化合物的n型掺杂剂成分、或者为包含第3主族元素的化合物的 p型掺杂剂成分。
由于成本低、来源丰富，优选所述掺杂剂成分A包含无机硼化合物成分、或者无机磷化合物成分。
由于考虑使用的安全性、低成本，进一步优选所述掺杂剂成分A包含的无机硼化合物为三氧化二硼或者硼酸，无机磷化合物为磷酸。
为了使掺杂剂成分分布均匀，优选所述高分子粘结剂B的分子结构重复单元中包含醇羟基。
为了更好地适用于旋转涂布和印刷涂布，优选所述高分子粘结剂B的重均分子量范围为1000～300000。出于易于热分解以及适用于旋转涂布的考虑，进一步优选所述高分子粘结剂B的重均分子量范围为3000～50000。
对于所述高分子粘结剂没有特别的限定，优选聚丙烯醇或聚乙烯醇。
出于增加聚乙烯醇、聚丙烯醇在溶剂中的溶解性的考虑，优选所述溶剂C由0～50％的水以及50～100％有机溶剂组成。
为了更好地适用于旋转涂布和印刷涂布，所述有机溶剂优选为沸点50～300摄氏度的有机溶剂。
对于有机溶剂没有特别的限定，优选1-甲氧基-2-丙醇、二丙酮醇、2-丙醇、正丁醇、3-甲氧基-3-甲基丁醇、二乙二醇甲乙醚、丙二醇、二乙二醇单丁醚、二丙二醇单甲醚、alpha-松油醇、二乙二醇单甲醚、一缩二乙二醇、甲醇、乙醇、1，4-二氧六环、丙酮、丁酮、乳酸甲酯或乳酸乙酯等。
出于对前述用于太阳能和半导体的材料的保存稳定性以及成本控制方面的考虑，优选所述掺杂剂成分A、高分子粘结剂B、聚硅氧烷和溶剂C的总添加量相对于浆料的总质量为2～30％。出于进一步提高浆料的保存稳定性和成本控制方面的考虑，进一步优选所述掺杂剂成分A、高分子粘结剂B、聚 硅氧烷和溶剂C的总添加量相对于浆料的总质量为5～20％。
本发明还公开了一种半导体基板的半导体单元的制造方法。其使用了前述用于太阳能和半导体的材料。前述方法含有如下a～c的工序，
a.将本发明的材料作为第一导电型杂质扩散组合物涂布在各半导体基板的一面，形成第一导电型杂质扩散组合物膜，
b.对a工序制备得到的形成有前述第一导电型杂质扩散组合物膜的半导体基板进行加热，使前述材料中的掺杂剂成分A中所含的第一导电型杂质向前述半导体基板中扩散，形成第一导电型杂质扩散层，
c.在含有第二导电型杂质的气体的气氛下加热前述半导体基板，使第二导电型的杂质向前述半导体基板中扩散，形成第二导电型杂质扩散层，
其中，在工序b以及c中，把两片一组的前述半导体基板的各自形成了第一导电型的杂质扩散组合物膜的面相向放置。其中，在工序b以及c中，把两片一组的前述半导体基板的各自形成了第一导电型的杂质扩散组合物膜的面相向放置是为了减少掺杂剂成分对未涂布面的污染以及在进行第二导电型杂质扩散时对第一导电型杂质扩散面的污染。
为了进一步防止第二导电型杂质对第一导电型杂质扩散面的污染，优选地，前述c工序在前述b工序之后将第一导电型杂质扩散组合物膜的热处理物作为掩膜来进行。
为了缩短工序、节约成本，优选地，前述c工序在前述b工序之后连续于所述b工序而进行。
为了降低对第一导电型扩散层的影响，优选地，前述c工序中，第二导电型杂质扩散层形成时的加热温度与前述b工序中第一导电型杂质扩散层形成时的温度相比低50～200℃。
为了调整半导体基板中第一导电型和第二导电型杂质的表面浓度，优选还含有d工序：在含有氧气的气氛下使半导体基板表面氧化。
为了缩短工序、降低成本，优选地，前述d工序在前述c工序之后连续于所述c工序而进行。
为了减少第二导电型杂质进入第一导电型扩散面，同时又能使第二导电型杂质可以均匀地沉积在第二导电型扩散面，优选地，在前述b以及c工序中，对前述两片一组的半导体基板的多个组而言，以各组中前述第一导电型的杂质扩散组合物膜形成的面之间的距离为W1，以相邻两组间前述第一导电型的杂质扩散组合物膜形成面与其相反面之间的距离为W2，W1和W2满足W1＜W2。
为了进一步减少第二导电型杂质进入第一导电型扩散面，优选地，前述b以及c工序中配置有多片半导体基板时，前述两片一组的半导体基板的前述第一导电型的杂质扩散组合物膜形成的面之间的距离W1为0mm。
为了使前述用于太阳能和半导体的材料中的有机物充分分解，以及提升前述形成的第一导电型杂质扩散组合物膜对第二导电型杂质的阻隔性，优选前述b工序为在含有氧气的气氛下进行。
为了降低切换气氛带来的工艺不稳定性，以及节约切换气氛需要的稳定时间，优选前述b工序中气氛中的氮气与氧气的比例与前述c工序中的气氛中氮气与氧气比例相同。
为了降低对第一导电型扩散层的影响，优选前述第一导电型为p型，前述第二导电型为n型。
本发明还公开了一种根据前述半导体单元制造方法制备的太阳能电池。
本发明的有益效果在于：
首先，本发明所提供的聚硅氧烷不仅在有机体溶剂中具有良好的溶解性，而且在水中的溶解性也得到了改善，使其适用范围得到扩大。
其次，使用本发明所提供的聚硅氧烷所制备的一种用于太阳能和半导体的材料，不仅具有良好扩散性，而且能够在一定程度上降低成本，同时也具有良好的阻隔性，也可以适用于具有掺杂功能的掩膜材料。在半导体(包含太阳能电池)的硼、磷扩散工艺中，不需要额外的掩膜层也可以得到目标结果，同时达到了缩短工艺降低成本的目标。
第三，使用本发明所提供的聚硅氧烷所制备的不含掺杂剂的材料，可以适用于不希望在掩模处发生掺杂的扩散工艺。
第四，使用本发明所提供的半导体单元和太阳能电池的制造工艺，可以进一步利用前述的用于太阳能和半导体的材料，本工艺中不仅利用了前述材料的优良阻隔性和优良扩散性，同时还通过制造工艺的改进进一步提升了对掺杂时掺杂剂成分A向涂布了本发明中用于太阳能和半导体的材料之外的区域扩散(即气中扩散)的抑制，缩短了工序数和工序时间。
附图说明
图1为阻隔性评价实验硅片放置方式。
图2为扩散性能以及气中扩散评测实验硅片放置方式。
图3由图3i、3ii和3iii组成为本发明的半导体单元的制造方法的一个示例的示意工序断面图。
图3i为一面上形成了第一导电型杂质扩散组合物膜的半导体基板断面图。
图3ii为上述一面上形成了第一导电型杂质扩散组合物膜的半导体基板 在扩散舟中的一种放置方式的断面图。
图3iii为上述图3ii的半导体基板热扩散后的断面图。
图4为第一导电型杂质扩散层形成时的半导体基板的设置的一个示例的示意断面图。
图5由图5i、5ii、5iii、5iv、5v、5vi和5vii组成为本发明的太阳能电池的制造方法的一个示例的示意工序断面图。
图5i为n型半导体基板断面图。
图5ii为一面上形成了p型杂质扩散组合物膜的半导体基板断面图。
图5iii为对上述图5ii的半导体基板进行了p型杂质扩散后的断面图。
图5iv为在图5iii的基础上进行了n型杂质扩散后的断面图。
图5v为将图5iv的半导体基板清洗后的断面图。
图5vi为在图5v的半导体基板上制备了防止反射层兼钝化层后的断面图。
图5vii为在图5vi的半导体基板上制备电极后的断面图。
图6为比较例的扩散舟上的半导体基板的配置示意断面图。
附图标记说明
1 半导体基板
2 第一导电型的杂质扩散组合物膜
3 一面上形成了第一导电型杂质扩散组合物膜的半导体基板
4 扩散舟
5 第一导电型的杂质扩散层
6 第一导电型的杂质扩散组合物膜的热处理物层
7 n型半导体基板
8 p型杂质扩散组合物膜
9 p型杂质扩散层
10 p型杂质扩散组合物膜的热处理物
11 磷硅玻璃层
12 n型杂质扩散层
13 防止反射层兼钝化层
14 p电极
15 n电极
16 扩散炉
具体实施方式
下面参照优选的实施方式对本发明进行说明。实施方式仅作例示之用，并不对发明加以限制，本发明的本质性内容并不必须具有实施方式中记述的所有特征。
本实施方式的聚硅氧烷的重复单元结构中含有醇羟基，其适用于(但不仅限于)本发明的用于太阳能和半导体的材料。前述聚硅氧烷的合成中，可使用烷氧基硅烷(1)、烷氧基硅烷(2)、有机溶剂(3)、水(4)、酸催化剂(5)(参见后述)，反应的监控可使用凝胶渗透色谱(GPC)测试分子量来判断反应终点。使用其制备的本发明的一种用于太阳能和半导体的材料含有掺杂剂成分(A)、高分子粘结剂(B)、聚硅氧烷和溶剂(C)。下面对本实施方式的聚硅氧烷的合成所涉及的化学品、以及本发明所述的一种用于太阳能和半导体的材料中各成分、使用了前述材料的半导体制造工艺、以及使用了本方法制备的太阳能电池进行说明进行说明。
《烷氧基硅烷(1)》
烷氧基硅烷(1)可以为一种或者多种，但是其分子结构中必须含有醇羟基，或者反应后可完全水解生成醇羟基的官能团(6)。作为官能团(6)可列举出酯官能团、环氧丙烷官能团、环氧丁烷官能团、易水解醚类官能团等。
作为烷氧基硅烷(1)可列举出3-缩水甘油基氧丙基三甲氧基硅烷、2-(3，4-环氧环己烷)乙基三甲氧基硅烷、3-缩水甘油基三甲氧基硅烷、3-(异丁烯酰氧)丙基三甲氧基硅烷、3-(甲基丙烯酰氧)丙基三甲氧基硅烷、三乙氧基(3-环氧丙基丙氧基)硅烷、二乙氧基(3-缩水甘油基氧基丙基)甲基硅烷、3-环氧丙氧丙基(二甲氧基)甲基硅烷、[8-(环氧丙基氧)-正辛基]三甲氧基硅烷等。
《烷氧基硅烷(2)》
烷氧基硅烷(2)可以为一种或者多种，但是其分子结构中不含上述烷氧基硅烷(1)中的官能团(6)。
作为烷氧基硅烷(2)可列举出苯基三甲氧基硅烷、甲基三甲氧基硅烷、乙基三甲氧基硅烷、乙烯基三甲氧基硅烷、甲基苯基二甲氧基硅烷、二甲基二甲氧基硅烷、二苯基二甲氧基硅烷、环己基甲基二甲氧基硅烷等。
《有机溶剂(3)》
有机溶剂(3)为在小于110℃强酸条件下不易水解的、室温下在100g水中溶解度高于30g、同时沸点高于110℃的有机溶剂。
作为有机溶剂(3)可列举出1-甲氧基-2-丙醇、二丙酮醇、2-丙醇、正丁醇、3-甲氧基-3-甲基丁醇、二乙二醇甲乙醚、丙二醇、二乙二醇单丁醚、二丙二醇单甲醚、alpha-松油醇、二乙二醇单甲醚、一缩二乙二醇等。
《水(4)》
水(4)作为参与烷氧基硅烷(1)以及烷氧基硅烷(2)水解反应的反应 物，可以列举出自来水、去离子水、超纯水等。
《酸催化剂(5)》
酸催化剂(5)用作为烷氧基硅烷(1)以及烷氧基硅烷(2)水解反应、并包括烷氧基硅烷(1)以及烷氧基硅烷(2)水解产物聚合的催化剂。除了对烷氧基硅烷(1)以及烷氧基硅烷(2)中与硅相连的烷氧基水解具有良好的催化作用之外，还需要具有对烷氧基硅烷(1)中与硅相连烷基类取代基中所含可完全水解生成醇羟基的官能团(5)水解的催化作用。
作为酸催化剂(5)可列举出盐酸、硫酸、磷酸(注：制备p型掺杂浆料时一般不使用磷酸)、硝酸、超强酸等。
《凝胶渗透色谱(GPC)》
凝胶渗透色谱(GPC)作为反应监控手段，使用的凝胶渗透色谱仪器为岛津(shimazu)S3-4100。色谱柱：TSKgel SuperHM-H、尺寸6.0mmI.D.×15cm、部件号0018001，微粒子尺寸3&5微米。测试条件为：流动相四氢呋喃、流量0.2毫升/分、柱温40℃、单个样品运行时间30分。制作标准曲线所使用的标准样品为聚苯乙烯。
《掺杂剂成分(A)》
掺杂剂成分(A)是半导体(包括太阳能电池)的制造中被普遍采用的化合物。掺杂剂成分(A)是包含含有第15族元素的化合物(本文中也简称为“第15族化合物”)的n型掺杂剂成分，或者是包含含有第13族元素的化合物(本文中也简称为“第13族化合物”)的p型掺杂剂成分。作为P型掺杂剂成分中所含的第13族化合物，可以列举出B(OH)3、B2O3、Al2O3等，通过在掺杂剂成分(A)中包含1种以上这些化合物，可以在半导体基板中形成p型或者高浓度p型杂质扩散层，所述扩散层本身也可以作为掩膜材料 阻挡其它杂质的污染。作为n型掺杂剂成分中所含的第15族化合物，可以列举出H3PO4、P2O5、Bi2O3等，通过在掺杂剂成分(A)中包含1种以上这些化合物，可以在半导体基板中形成N型或者高浓度N型杂质扩散层，所述扩散层本身也可以作为掩膜材料阻挡其它杂质的污染。
《高分子粘结剂(B)》
高分子粘结剂(B)具有将上述掺杂剂成分均匀分布在掺杂浆料以及掩膜材料烘干后所形成的固体成分里的功能，这样有助于对目标半导体基板的掺杂更均匀。
上述高分子粘结剂(B)为聚丙烯酸系非硅高分子，或者重复单元含有醇羟基的非硅系高分子。其中优选重复单元含有醇羟基的非硅系高分子，例如聚乙烯醇、聚丙烯醇等。
《聚硅氧烷》
聚硅氧烷为本发明所提供的分子重复单元中含有醇羟基的硅氧烷。其中所含的硅原子在高分子氧化分解后形成的硅氧化物可以起到良好的阻隔作用来防止其他元素对浆料涂布面的污染，同时也可以减少本发明的材料所含有的掺杂剂成分向外扩散，从而减少对外的污染，以及通过结合掺杂剂成分来提升掺杂性能。另外，其中含有的醇羟基也可以辅助高分子粘结剂(B)使掺杂剂成分的分布更均匀，同时改善聚硅氧烷在水溶性掺杂浆料以及掩膜材料中的溶解性，从而可以在不影响掺杂剂成分的分布均一性和稳定性的情况下，根据实际要求在更大的范围内调整掺杂剂成分和聚硅氧烷的添加量。
《溶剂(C)》
溶剂(C)可以是不添加水的单一有机溶剂、有机溶剂的混合溶剂，也可以是有机溶剂与水的混合溶剂。单一溶剂的情况下优选沸点高于100℃的有 机溶剂，从而防止溶剂挥发过而影响涂膜的质量。在混合溶剂的情况下也可以选用沸点低于100℃的有机溶剂，如果使用了沸点低于100℃的有机溶剂，同时其中必须含有相对于溶剂总质量达到40质量％以上的沸点高于100℃的有机溶剂与水的混合溶剂。为了防止在涂膜工艺中，溶剂挥发过快影响性能，即使在混合溶剂中同样优选沸点高于100℃的溶剂。
溶剂(C)所含有的有机溶剂可列举出1-甲氧基-2-丙醇、二丙酮醇、2-丙醇、正丁醇、3-甲氧基-3-甲基丁醇、二乙二醇甲乙醚、丙二醇、二乙二醇单丁醚、二丙二醇单甲醚、alpha-松油醇、二乙二醇单甲醚、一缩二乙二醇、甲醇、乙醇、1，4-二氧六环、丙酮、丁酮、乳酸甲酯、乳酸乙酯等。
《半导体基板的半导体单元的制造方法》
本发明半导体单元的制造方法可以是下述使用了多片的半导体基板的半导体单元的制造方法，前述方法含有如下a～c的工序，
工序a.在各半导体基板的一面上涂布第一导电型杂质扩散组合物，形成第一导电型杂质扩散组合物膜，
工序b.对形成了前述第一导电型杂质扩散组合物膜的半导体基板进行加热，使前述第一导电型杂质向前述半导体基板中扩散，形成第一导电型杂质扩散层，
工序c.在含有第二导电型杂质的气体的气氛下加热前述半导体基板，使第二导电型的杂质向前述半导体基板中扩散，形成第二导电型杂质扩散层，
其中，在工序b以及c中，将两片一组的半导体基板的各自形成了第一导电型杂质扩散组合物膜的面相向放置。
(a工序)
如图3i所示，在半导体基板1的一面上涂布第一导电型杂质扩散组合物 形成第一导电型杂质扩散组合物膜2。
第一导电型杂质扩散组合物的涂布方法不做特别限定，适用于半导体基板的众所周知的涂布方法都可使用。例如，可以使用丝网印刷、照相凹版印刷等的印刷法、旋转涂布法、板刷涂布、喷雾法、刮浆刀法、辊涂法或喷墨打印法等。
如图3i中虽然对半导体基板1的一面的整个面上涂布第一导电型杂质扩散组合物的形态进行了说明，但是在整个面的一部分上涂布第一导电型杂质扩散组合物也是可以的。
还可以在半导体基板1的一面上形成了第一导电型杂质扩散组合物膜2之后设置去除第一导电型杂质扩散组合物膜2中的溶剂的至少一部分的干燥工序。干燥工序中，例如，加热至100摄氏度～300摄氏度处理，使溶剂的至少一部分挥发。
作为半导体基板1，没有特别的限制，例如可以列举出杂质浓度1015～1016个原子/cm3的n型单晶硅、多晶硅以及混合了锗、碳等其它元素的结晶硅基板。而且，还可以使用p型结晶硅或硅以外的半导体。
半导体基板1的厚度为50～300μm，外形为优选一条边为100～250mm的四方形。并且，为了去除切片损伤和自然氧化膜，优选地，其经过以氢氟酸溶液和碱溶液等进行的表面刻蚀处理。
而且，使用碱性溶液刻蚀半导体基板的两面，优选在两面上形成被称作绒面构造的微细凹凸构造。绒面构造为，例如是通过将硅基板浸泡在含有氢氧化钾和异丙醇的80摄氏度的溶液中形成的。
对于第一导电型杂质扩散组合物，没有特别限制，优选本发明所提供的掺杂浆料以及掩膜材料。
(b工序)
如图3ii所示，将一面上形成了第一导电型杂质扩散组合物膜2的半导体基板3设置为两片一组的形式，将各自形成了第一导电型杂质扩散组合物膜2的面相向设置在扩散舟4中。
扩散舟4为了设置半导体基板而设有凹槽。扩散舟的凹槽尺寸和间距没有特别限定。扩散舟相对于水平方向有倾斜也是可以的。扩散舟的材质为能够耐扩散温度之外没有特别限定，但是优选石英。
如图3iii所示，将设置了半导体基板3的扩散舟4在扩散炉16中加热，使第一导电型杂质向半导体基板1扩散，形成第一导电型杂质扩散层5。
这时，因为两片一组的半导体基板如前述设置，即使杂质从杂质扩散组合物膜2向气体中扩散，这样也很难到达半导体基板的第一导电型杂质扩散组合物膜2形成面的反面。
第一导电型杂质扩散层5形成时的加热处理温度以及时间可以根据杂质扩散浓度、扩散深度等可以得到所期望的扩散特性适当设定。例如，可以设定800摄氏度以上1200摄氏度以下加热扩散1～120分钟。
对于为了形成第一导电型杂质扩散层5的加热处理的气体气氛没有特别的限制，但是优选氮气、氧气、氩气、氦气、氙气、氖气、氪气等的混合气氛，进一步优选氮气和氧气的混合气氛，特别是优选氧气含量为体积含量5％以下的氮气和氧气的混合气氛。为了可以抑制向外扩散，优选在混合气氛中存在氧气的气氛下进行第一导电型的杂质扩散。
对两片一组的半导体基板的第一导电型杂质扩散组合物膜2形成的面之间的距离W1没有特别限定，优选5mm以下，最好是在1mm以下。
例如，如图4所示，可以在扩散舟4的一个凹槽内设置两片一组的半导 体基板，为了有抑制向外扩散的倾向，优选两片一组的半导体基板的各第一导电型的杂质扩散组合物膜2形成的面之间的距离W1为短的距离。进一步优选所述第一导电型的杂质扩散组合物膜2形成的面之间的距离W1为0mm，即间隔实质上为0mm(实质为接触)。
对于半导体基板相邻两组间的前述第一导电型的杂质扩散组合物膜形成面的反面之间的距离W2没有特别的限定，优选1～5mm，进一步优选1～3mm。
优选地，对于前述两片一组的半导体基板的多个组而言，以各组中前述第一导电型的杂质扩散组合物膜形成的面之间的距离为W1，以相邻两组间前述第一导电型的杂质扩散组合物膜形成面的反面之间的距离为W2，W1和W2满足W1＜W2。如上所述，连续于b工序进行c工序的情况下，扩散舟上的半导体基板的设置不变，可以向半导体基板的另一面扩散杂质。
并且，优选地，在b工序之前，例如，将在一面上形成了第一导电型杂质扩散组合物膜的半导体基板3在低于扩散时的热处理温度下且在含有氧气的气氛下进行加热处理，以至少除去第一导电型杂质扩散组合物膜2中粘结剂树脂等有机成分中的一部分。第一导电型的杂质扩散组合物膜2中的粘结剂树脂等有机成分被除去至少一部分的情况下，半导体基板上的第一导电型杂质扩散组合物膜中的杂质成分的浓度能够提高，第一导电型的杂质的扩散性也容易得到提高。
对于b工序的气体氛围没有特别限制，但是优选氮气、氧气、氩气、氦气、氙气、氖气、氪气等的混合气氛，进一步优选含有氧气的混合气氛。优选在含有氧气的气氛下进行，这样第一导电型的杂质扩散组合物膜中的粘结剂等有机成分的热分解将更容易。
气体氛围中的氧气的含量没有特别的限定，但是优选体积含量20％以下， 进一步优选体积含量5％以下。
(c工序)
c工序的扩散舟上的半导体基板的设置为，与b工序中说明的相同。即，将两片一组的半导体基板的形成有各自的第一导电型杂质扩散组合物膜的面相向设置。
对于两片一组的半导体基板的第一导电型的杂质扩散组合物膜2形成的面之间的距离W1没有特别限定，优选5mm以下，进一步优选1mm以下。
例如，图4所示，可以在扩散舟4的一个凹槽内设置两片一组的半导体基板，为了有抑制向外扩散的倾向，优选两片一组的半导体基板的各第一导电型的杂质扩散组合物膜2形成的面之间的距离W1为短的距离。进一步优选地，所述第一导电型的杂质扩散组合物膜2形成的面之间的距离W1为0mm，即此间隔实质为0mm(实质为接触)。
对于半导体基板相邻组间的前述第一导电型的杂质扩散组合物膜形成面的反面之间的距离W2没有特别限定，优选1～5mm，进一步优选1～3mm。
优选地，对于前述两片一组的半导体基板的多个组而言，以各组中前述第一导电型的杂质扩散组合物膜形成的面之间的距离为W1，以相邻两组间前述第一导电型的杂质扩散组合物膜形成面的反面之间的距离为W2，W1和W2满足W1＜W2。如上所述，连续于b工序进行c工序的情况下，扩散舟上的半导体基板的设置不变，可以向半导体基板的另外一面扩散第二导电型杂质。
c工序中，在流入含有第二导电型杂质的气体的同时，加热半导体基板，形成第二导电型的杂质扩散层。
作为含有第二导电型杂质的气体，n型的情况下，可以为POCl3气体，p 型的情况下，可列举为BBr3、BCl3等气体。POCl3气体例如为向POCl3溶液中鼓泡通入氮气或者氮气/氧气的混合气体，或者可以加热POCl3溶液得到。
加热温度为，优选750摄氏度～1050摄氏度，进一步优选800摄氏度～1000摄氏度。
对于气体气氛没有特别限定，但是优选氮气、氧气、氩气、氦气、氙气、氖气、氪气等的混合气氛，进一步优选氮气和氧气的混合气氛，特别优选氧气的体积含有率5％以下的氮气和氧气的混合气氛。
而且，因为能够缩短气体气氛的变更的工序时间，所以优选不改变b工序的气氛即进行c工序。特别是，b工序中气体气氛中的氮气和氧气的比例和c工序中气体气氛中的氮气和氧气的比例相同。这种情况下的优选比率为：氧气∶氮气的体积比＝1∶99～5∶95。
如图3iii所示，b工序后，第一导电型的杂质扩散层5的上面残留有第一导电型杂质扩散组合物膜的热处理物层6。优选将此作为对含有第二导电型杂质气体的掩模，来进行c工序。这样做的话，可以抑制第二导电型杂质向第一导电型的杂质扩散层5中混入。
b工序和c工序哪个先进行都是可以的，或者c工序和b工序也可以同时进行。将第一导电型的杂质扩散组合物膜的热处理物层作为掩膜来使用的情况下，优选c工序在b工序的后面进行。
而且，优选在b工序之后连续于b工序而进行c工序。例如，b工序后，优选不从烧成炉里取出扩散舟即直接进行c工序。在b工序后，连续于b工序而进行c工序的话，称作在b的工序之后连续于b工序而进行c工序。
所述c工序中形成第二导电型的杂质扩散层时的加热温度优选比在前述b的工序形成第一导电型的杂质扩散层时的加热温度低50～200摄氏度。通过 使得c工序中形成第二导电型的杂质扩散层时的加热温度相比b工序中形成第一导电型的杂质扩散层时的加热温度低50～200摄氏度，在b工序之后连续于b工序而进行c工序的情况下，可以使对在b工序中形成的第一导电型杂质扩散层的加热的影响得以最小化，可以容易地控制第一导电型杂质的扩散。
c工序中，因为与使用含有p型杂质的气体进行扩散时相比，使用含有n型杂质的气体进行扩散时的加热温度可以实现低温，所以优选第一导电型为p型，第二导电型为n型。
而且，本发明的半导体单元的制造方法为，优选含有下述d的工序。
d.含有氧气气氛下的使半导体基板表面氧化的工序。
(d工序)
对于d工序进行的时间没有特别的限定，优选b工序之后或者c工序之后可以进行d工序。优选在c的工序之后连续于c工序而进行d工序。这样做的话，可以除去在本来不需要发生扩散的位置因向外扩散而产生的的扩散层(污染层)。在c工序后连续于c工序而进行d工序的话，称作在c的工序之后连续于c工序而进行d工序。
气氛含有氧气即可，对气氛没有特别的限定，可以使用氮气、氩气、氦气、氙气、氖气、氪气等与氧气的混合气氛。优选氮气和氧气的混合气氛，进一步优选氧气体积含量20％以上的氮气和氧气的混合气氛，特别优选纯氧气气氛。氧气含量越多，越可以提高氧化速度。
这些工序之后，可以使用已知的方法来制造半导体单元。这些方法没有特别的限定，例如可以列举以下的方法作为一个例子。
在半导体基板的两面上，形成防止反射层或者钝化层。这些层可以使用各种已知的材料。这些层单层也可以多层也可以。例如，可以使用氧化硅层、 氧化铝层、SiNx层、非晶硅层层叠而成。这些层可以通过等离子CVD法、ALD(原子层堆积)法等的蒸镀法、或者涂布法形成。
而且，形成为兼具反射防止层与钝化层功能的层也是可以的。作为那样的层，可以列举通过等离子CVD法形成的氮化物层。
在反射防止层与半导体基板之间还可以存在有含氧化硅、氧化铝等的表面保护层。而且，即使部分改变反射防止层的组成也是可以的。
反射防止层在受光面以及内面的整面或者一部分的领域上形成也是可以的。在杂质扩散层的上表面，在反射防止层上设置接触孔也是可以的。这样做的话，接下来形成的电极和杂质扩散层可以形成电接触。对接触孔的形成方法没有限定，但是优选刻蚀。刻蚀中，针对反射防止层的材质可以采用合适的物质，例如，可以列举氟化铵等。
适当的场合中，烧穿法也可以使用。烧穿法为：反射防止层之上形成电极之后，利用烧成过程使玻璃粒子熔融，反射防止层分解的同时电极和半导体基板粘合在一起的方法，其被成为烧成贯穿，即烧穿法。这种情况下，适用于反射防止层的材料为氮化硅。
接下来，在半导体基板的两面上形成电极。没有特别限定，可以使用电极的形成中通常使用的方法。
利用烧穿法的情况下，例如，可以使用含有金属粒子以及玻璃粒子的表面电极用金属浆料。可以赋予表面电极用金属浆料以使其在形成有杂质扩散层的领域上形成所希望的图案，利用热处理使金属粒子贯通反射防止层或者钝化层，从而在杂质扩散层上电极形成领域上形成表面电极。作为表面电极用金属浆料，例如，可以使用该技术领域常用的银浆等。
图5中，将模式化展示本实施形态所涉及的两面受光型太阳能电池单元 制造方法的一个例子的工序图作为断面图示出。但是，本发明不受该工序图的任何限制。
半导体基板为n型半导体基板，第一导电型为p型，第二导电型为n型时的例子，使用图5来说明。
首先，如图5i所示准备了厚度为50μm～300μm左右的n型半导体基板7。该n型半导体基板7是通过将使用CZ(Czochrzlski)法、FZ(Floating Zone)法、EFG(Edge Difined Film Growth)法、铸造法等形成的单结晶或者多结晶的硅锭切片而成的，例如，其中具有浓度为1*1015个原子/cm3～1*1019个原子/cm3的n型杂质(磷等)。
优选n型半导体基板7经碱水溶液清洗。利用碱水溶液清洗，可以去除n型半导体基板7的表面上存在的有机物、粒子等，钝化的效果也可以得到提高。
作为通过碱性水溶液清洗的方法，可以举例一般的众所周知的RCA清洗法等。例如，将n型半导体基板7浸入到氨水-过氧化氢的混合溶液中，在60摄氏度～80摄氏度下处理，可以去除有机物以及粒子。清洗时间为，优选10秒～10分钟，进一步优选30秒～5分钟。
n型半导体基板7为，通过碱刻蚀等方法，在两面上，例如优选形成金字塔构造的绒面构造(图示无)。由此，可以抑制太阳光的反射。
接着，如图5ii所示，在一面上涂布p型杂质扩散组合物，形成p型杂质扩散组合物膜8。接着，如图5iii中所示的那样，将半导体基板7以各自的杂质扩散组合物膜形成的面相对的方式一起设置到扩散舟4中。
然后，进行热扩散形成p型扩散层9。这个时候，p型杂质扩散组合物膜8通过以热扩散为目的的热处理而形成热处理物10。对于热处理温度优选800 摄氏度～1200摄氏度。
接下来如图5iv所示，向POCl3溶液中通入氮气或者氮气与氧气的混合气氛鼓泡的同时，将n型半导体基板7加热到750摄氏度～950摄氏度，磷硅玻璃层11和n型杂质扩散层12同时形成。p型杂质扩散组合物膜的热处理物10作为掩膜层，可以抑制磷向p型杂质扩散层9形成的内面扩散。之后，在含有氧气的气氛下，对半导体基板进行氧化过程，以使得磷污染层氧化。经氧化的污染层p型杂质扩散组合物膜的热处理物10以及磷硅玻璃层11是一体化的(图中未示出)。
之后，如图5v所示，除去p型杂质扩散组合物膜的热处理物10以及磷硅玻璃11。作为除去的方法，例如可以列举浸泡在氢氟酸等的刻蚀液中。
之后，如图5vi所示，受光面以及内面上分别形成了防止反射层兼钝化层13。关于防止反射层兼钝化层13，可参见前文所述，可以列举优选例氮化硅层、氧化钛层、氧化硅层或氧化铝层等。
此实施形态中，防止反射层兼钝化层13在受光面以及内面的一部分领域上形成。
之后，如图5vii所示，在受光面以及内面的各自的上表面，在不存在防止反射层兼钝化层13的部分上形成p电极14以及n电极15。电极可通过赋予了可形成电极的浆料后进行加热处理来形成。
图5中，举例说明了在n型半导体基板上的防止反射层兼钝化层13上预先设置缺失部位、并在其上形成p电极14以及n电极15的方法。但是，防止反射层兼钝化层13为在整个面上形成的情况下，作为电极形成用浆料使用含有具烧穿性玻璃粒子的浆料，烧成后贯穿防止反射层兼钝化层13，可以实现杂质扩散层和电极的欧姆接触。如上操作，可以得到太阳能单元。
《聚硅氧烷的合成》
制备例1：
Figure PCTCN2017098627-appb-000018
室温下，在大小合适的反应器中依次加入104.98克3-缩水甘油基氧丙基三甲氧基硅烷、1.23克甲基三甲氧基硅烷和130.47克二乙二醇单甲醚。加热升温至40℃，然后滴加浓硫酸(0.23克)和水(40.47克)的混合溶液。滴加完成后继续在40℃搅拌1小时。然后升温至70℃，并搅拌1小时20分钟。然后升温至100℃，并搅拌1小时。之后升高油浴温度至120度，搅拌。油浴升温至120℃之后使用GPC检测反应直至达到目标重均分子量4500±200克/摩尔。冷却到40℃以下后，转移到其它容器-20～40℃保存。得到本发明提供的聚硅氧烷A021。
制备例2：
Figure PCTCN2017098627-appb-000019
室温下，在大小合适的反应器中依次加入41.21克3-缩水甘油基氧丙基三甲氧基硅烷、95.02克甲基三甲氧基硅烷和130.47克二乙二醇单甲醚。加热升温至40℃，然后滴加浓硫酸(0.44克)和水(78.47克)的混合溶液。滴加完成后继续在40℃搅拌1小时。然后升温至70℃，并搅拌1小时20分钟。然后升温至100℃，并搅拌1小时。之后升高油浴温度至120度，搅拌。油浴升温至120℃之后使用GPC检测反应直至达到目标重均分子量4500±200克/摩尔。冷却到40℃以下后，转移到其它容器-20～40℃保存。得到本发 明提供的聚硅氧烷A021。
制备例3：
Figure PCTCN2017098627-appb-000020
室温下，在大小合适的反应器中依次加入98.07克3-缩水甘油基氧丙基三甲氧基硅烷、9.14克苯基三甲氧基硅烷和130.47克二乙二醇单甲醚。加热升温至40℃，然后滴加浓硫酸(0.23克)和水(41.49克)的混合溶液。滴加完成后继续在40℃搅拌1小时。然后升温至70℃，并搅拌1小时20分钟。然后升温至100℃，并搅拌1小时。之后升高油浴温度至120度，搅拌。油浴升温至120℃之后使用GPC检测反应直至达到目标重均分子量4500±200克/摩尔。冷却到40℃以下后，转移到其它容器-20～40℃保存。得到本发明提供的聚硅氧烷A156。
制备例4：
Figure PCTCN2017098627-appb-000021
室温下，在大小合适的反应器中依次加入61.83克3-缩水甘油基氧丙基三甲氧基硅烷、51.88克苯基三甲氧基硅烷和130.47克二乙二醇单甲醚。加热升温至40℃，然后滴加浓硫酸(0.26克)和水(47.09克)的混合溶液。滴加完成后继续在40℃搅拌1小时。然后升温至70℃，并搅拌1小时20分钟。然后升温至100℃，并搅拌1小时。之后升高油浴温度至120度，搅拌。油浴升温至120℃之后使用GPC检测反应直至达到目标重均分子量4500± 200克/摩尔。冷却到40℃以下后，转移到其它容器-20～40℃保存。得到本发明提供的聚硅氧烷A156。
制备例5：
Figure PCTCN2017098627-appb-000022
室温下，在大小合适的反应器中依次加入102.93克2-(3，4-环氧环己烷)乙基三甲氧基硅烷、2.64克二甲基二甲氧基硅烷和130.47克二乙二醇单甲醚。加热升温至40℃，然后滴加浓硫酸(0.22克)和水(39.58克)的混合溶液。滴加完成后继续在40℃搅拌1小时。然后升温至70℃，并搅拌1小时30分钟。然后升温至100℃，并搅拌1小时。之后升高油浴温度至120度，搅拌。油浴升温至120℃之后使用GPC检测反应直至达到目标重均分子量4000±200。冷却到40℃以下后，转移到其它容器-20～40℃保存。得到本发明提供的聚硅氧烷A081。
制备例6：
Figure PCTCN2017098627-appb-000023
室温下，在大小合适的反应器中依次加入89.91克2-(3，4-环氧环己烷)乙基三甲氧基硅烷、16.63克甲基苯基二甲氧基硅烷和130.47克二乙二醇单甲醚。加热升温至40℃，然后滴加浓硫酸(0.23克)和水(41.05克)的混合溶液。滴加完成后继续在40℃搅拌1小时。然后升温至70℃，并搅拌1小时30分钟。然后升温至100℃，并搅拌1小时。之后升高油浴温度至120度， 搅拌。油浴升温至120℃之后使用GPC检测反应直至达到目标重均分子量1000±200。冷却到40℃以下后，转移到其它容器-20～40℃保存。得到本发明提供的聚硅氧烷A126。
制备例7：
Figure PCTCN2017098627-appb-000024
室温下，在大小合适的反应器中依次加入67.38克3-缩水甘油基氧丙基三甲氧基硅烷、40.43克苯基三甲氧基硅烷和130.47克二乙二醇单甲醚。加热升温至40℃，然后滴加浓硫酸(0.26克)和水(45.87克)的混合溶液。滴加完成后继续在40℃搅拌1小时。然后升温至70℃，并搅拌1小时20分钟。然后升温至100℃，并搅拌1小时。之后升高油浴温度至120度，搅拌。油浴升温至120℃之后使用GPC检测反应直至达到目标重均分子量10800±200克/摩尔。冷却到40℃以下后，转移到其它容器-20～40℃保存。得到本发明提供的聚硅氧烷A159。
制备例8：
Figure PCTCN2017098627-appb-000025
室温下，在大小合适的反应器中依次加入85.40克3-缩水甘油基氧丙基三甲氧基硅烷、20.7克甲基三甲氧基硅烷和130.47克二乙二醇单甲醚。加热升温至40℃，然后滴加浓硫酸(0.25克)和水(44.21克)的混合溶液。滴加完成后继续在40℃搅拌1小时。然后升温至70℃，并搅拌1小时20分钟。 然后升温至100℃，并搅拌1小时。之后升高油浴温度至120度，搅拌。油浴升温至120℃之后使用GPC检测反应直至达到目标重均分子量3000±200克/摩尔。冷却到40℃以下后，转移到其它容器-20～40℃保存。得到本发明提供的聚硅氧烷A029。
制备例9：
Figure PCTCN2017098627-appb-000026
室温下，在大小合适的反应器中依次加入112.47克3-缩水甘油基氧丙基三甲氧基硅烷和130.47克二乙二醇单甲醚。加热升温至40℃，然后滴加浓硫酸(0.24克)和水(42.83克)的混合溶液。滴加完成后继续在40℃搅拌1小时。然后升温至70℃，并搅拌1小时20分钟。然后升温至100℃，并搅拌1小时。之后升高油浴温度至120度，搅拌。油浴升温至120℃之后使用GPC检测反应直至达到目标重均分子量6800±200克/摩尔。冷却到40℃以下后，转移到其它容器-20～40℃保存。得到本发明提供的聚硅氧烷A221。
制备例10：
Figure PCTCN2017098627-appb-000027
室温下，在大小合适的反应器中依次加入112.47克3-缩水甘油基氧丙基三甲氧基硅烷和130.47克二乙二醇单甲醚。加热升温至40℃，然后滴加浓硫酸(0.24克)和水(42.83克)的混合溶液。滴加完成后继续在40℃搅拌1小时。然后升温至70℃，并搅拌1小时20分钟。然后升温至100℃，并搅拌1小时。之后升高油浴温度至120度，搅拌。油浴升温至120℃之后使用GPC 检测反应直至达到目标重均分子量4500±200克/摩尔。冷却到40℃以下后，转移到其它容器-20～40℃保存。得到本发明提供的聚硅氧烷(A221)。
制备例11：
Figure PCTCN2017098627-appb-000028
室温下，在大小合适的反应器中依次加入112.47克3-缩水甘油基氧丙基三甲氧基硅烷和130.47克3-甲氧基-3-甲基丁醇。加热升温至40℃，然后滴加浓硫酸(0.24克)和水(42.83克)的混合溶液。滴加完成后继续在40℃搅拌1小时。然后升温至70℃，并搅拌1小时20分钟。然后升温至100℃，并搅拌1小时。之后升高油浴温度至120度，搅拌。油浴升温至120℃之后使用GPC检测反应直至达到目标重均分子量4500±200克/摩尔。冷却到40℃以下后，转移到其它容器-20～40℃保存。得到本发明提供的聚硅氧烷(A221)。
制备例12：
Figure PCTCN2017098627-appb-000029
室温下，在大小合适的反应器中依次加入112.47克3-缩水甘油基氧丙基三甲氧基硅烷和130.47克3-甲氧基-3-甲基丁醇。加热升温至40℃，然后滴加浓硫酸(0.24克)和水(42.83克)的混合溶液。滴加完成后继续在40℃搅拌1小时。然后升温至70℃，并搅拌1小时20分钟。然后升温至100℃，并搅拌1小时。之后升高油浴温度至120度，搅拌。油浴升温至120℃之后使用GPC检测反应直至达到目标重均分子量8600±200克/摩尔。冷却到40℃以下后，转移到其它容器-20～40℃保存。得到本发明提供的聚硅氧烷(A221)。
制备例13：
Figure PCTCN2017098627-appb-000030
室温下，在大小合适的反应器中依次加入112.47克2-(3，4-环氧环己烷)乙基三甲氧基硅烷和130.47克3-甲氧基-3-甲基丁醇。加热升温至40℃，然后滴加浓硫酸(0.23克)和水(41.08克)的混合溶液。滴加完成后继续在40℃搅拌1小时。然后升温至70℃，并搅拌1小时20分钟。然后升温至100℃，并搅拌1小时。之后升高油浴温度至120度，搅拌。油浴升温至120℃之后使用GPC检测反应直至达到目标重均分子量9000±200。冷却到40℃以下后，转移到其它容器-20～40℃保存。得到本发明提供的聚硅氧烷(A251)。
制备例14：
Figure PCTCN2017098627-appb-000031
室温下，在大小合适的反应器中依次加入112.47克3-缩水甘油基三甲氧基硅烷和130.47克二乙二醇单甲醚。加热升温至40℃，然后滴加浓硫酸(0.32克)和水(56.78克)的混合溶液。滴加完成后继续在40℃搅拌1小时。然后升温至70℃，并搅拌1小时30分钟。然后升温至100℃，并搅拌1小时。之后升高油浴温度至120度，搅拌。油浴升温至120℃之后使用GPC检测反应直至达到目标重均分子量1000±200。冷却到40℃以下后，转移到其它容器-20～40℃保存。得到本发明提供的聚硅氧烷(A211)。
制备例15：
Figure PCTCN2017098627-appb-000032
室温下，在大小合适的反应器中依次加入112.47克甲基-3-缩水甘油基氧丙基二甲氧基硅烷和130.47克3-甲氧基-3-甲基丁醇。加热升温至40℃，然后滴加浓硫酸(0.23克)和水(41.65克)的混合溶液。滴加完成后继续在40℃搅拌1小时。然后升温至70℃，并搅拌1小时20分钟。然后升温至100℃，并搅拌1小时。之后升高油浴温度至120度，搅拌。油浴升温至120℃之后使用GPC检测反应直至达到目标重均分子量10800±200克/摩尔。冷却到40℃以下后，转移到其它容器-20～40℃保存。得到本发明提供的聚硅氧烷(A222)。
制备例16：
Figure PCTCN2017098627-appb-000033
室温下，在大小合适的反应器中依次加入112.47克甲基-3-缩水甘油基氧丙基二甲氧基硅烷和130.47克3-甲氧基-3-甲基丁醇。加热升温至40℃，然后滴加浓硫酸(0.22克)和水(40.83克)的混合溶液。滴加完成后继续在40℃搅拌1小时。然后升温至70℃，并搅拌1小时20分钟。然后升温至100℃，并搅拌1小时。之后升高油浴温度至120度，搅拌。油浴升温至120℃之后使用GPC检测反应直至达到目标重均分子量4500±200克/摩尔。冷却到40℃以下后，转移到其它容器-20～40℃保存。得到本发明提供的聚硅氧烷(A232)。
制备例17：
Figure PCTCN2017098627-appb-000034
室温下，在大小合适的反应器中依次加入160克甲基-2-羟乙基二甲氧基硅烷和130克3-甲氧基-3-甲基丁醇。加热升温至40℃，然后添加对甲苯磺酸(0.4克)和水(60克)的混合溶液。滴加完成后继续在40℃搅拌1小时。然后升温至70℃，并搅拌1小时20分钟。然后升温至100℃，并搅拌1小时。之后升高油浴温度至120度，搅拌。油浴升温至120℃之后使用GPC检测反应直至达到目标重均分子量4500±200克/摩尔。冷却到40℃以下后，转移到其它容器-20～40℃保存。得到本发明提供的聚硅氧烷(A182)。
制备例18：
Figure PCTCN2017098627-appb-000035
室温下，在大小合适的反应器中依次加入120克双(3-缩水甘油基氧丙基)二甲氧基硅烷和130.47克3-甲氧基-3-甲基丁醇。加热升温至40℃，然后滴加浓硫酸(0.32克)和水(75克)的混合溶液。滴加完成后继续在40℃搅拌1小时。然后升温至70℃，并搅拌1小时20分钟。然后升温至100℃，并搅拌1小时。之后升高油浴温度至120度，搅拌。油浴升温至120℃之后使用GPC检测反应直至达到目标重均分子量4500±200克/摩尔。冷却到40℃以下后，转移到其它容器-20～40℃保存。得到本发明提供的聚硅氧烷(A262)。
制备例19：
Figure PCTCN2017098627-appb-000036
室温下，在大小合适的反应器中依次加入70克3-缩水甘油基氧丙基三甲氧基硅烷、40克甲基-2-羟乙基二甲氧基硅烷和130.47克3-甲氧基-3-甲基丁醇。加热升温至40℃，然后滴加对甲苯磺酸(0.32克)和水(60克)的混合溶液。滴加完成后继续在40℃搅拌1小时。然后升温至70℃，并搅拌1小时20分钟。然后升温至100℃，并搅拌1小时。之后升高油浴温度至120度，搅拌。油浴升温至120℃之后使用GPC检测反应直至达到目标重均分子量4500±200克/摩尔。冷却到40℃以下后，转移到其它容器-20～40℃保存。得到本发明提供的聚硅氧烷(A266)。
《用于太阳能和半导体的材料的制备》
本发明的用于太阳能和半导体的材料的包含但不仅限于掺杂浆料以及掩膜材料。
实施例1：
室温下，在大小合适的反应器中依次加入58.55克3-甲氧基-3-甲基丁醇和4.22克聚乙烯醇。加热升温至80℃，然后滴加36.00克水。滴加完成后继续在80℃搅拌直至聚乙烯醇完全溶解。然后添加0.73克三氧化二硼，并在80℃继续搅拌1小时。然后冷却到40℃以下，滴加16.67克上述制备例1合成的聚硅氧烷。持续搅拌1小时后，转移到其它容器并在-20～40℃保存。得到本发明提供的的一种用于太阳能和半导体的材料。
实施例2：
室温下，在大小合适的反应器中依次加入58.55克3-甲氧基-3-甲基丁醇 和4.22克聚乙烯醇。加热升温至80℃，然后滴加36.00克水。滴加完成后继续在80℃搅拌直至聚乙烯醇完全溶解。然后添加0.73克三氧化二硼，并在80℃继续搅拌1小时。然后滴加16.67克上述制备例1合成的聚硅氧烷。然后加入0.375克三氧化二硼，持续搅拌1小时后，转移到其它容器并在-20～40℃保存。得到本发明提供的的一种用于太阳能和半导体的材料。
实施例3：
室温下，在大小合适的反应器中依次加入58.55克3-甲氧基-3-甲基丁醇和4.22克聚乙烯醇。加热升温至80℃，然后滴加36.00克水。滴加完成后继续在80℃搅拌直至聚乙烯醇完全溶解。然后添加0.73克三氧化二硼，并在80℃继续搅拌1小时。然后滴加16.67克上述制备例3合成的聚硅氧烷。然后加入0.75克三氧化二硼，持续搅拌1小时后，转移到其它容器并在-20～40℃保存。得到本发明提供的的一种用于太阳能和半导体的材料。
实施例4：
室温下，在大小合适的反应器中依次加入58.55克3-甲氧基-3-甲基丁醇和4.22克聚乙烯醇。加热升温至80℃，然后滴加36.00克水。滴加完成后继续在80℃搅拌直至聚乙烯醇完全溶解。然后添加0.26克85重量％的磷酸水溶液。然后滴加16.67克上述制备例3合成的聚硅氧烷，并在80℃继续搅拌1小时。冷却到40℃以下后，转移到其它容器-20～40℃保存。得到本发明提供的的一种用于太阳能和半导体的材料。
实施例5：
室温下，在大小合适的反应器中依次加入58.55克3-甲氧基-3-甲基丁醇和4.22克聚乙烯醇。加热升温至80℃，然后滴加36.00克水。滴加完成后继续在80℃搅拌直至聚乙烯醇完全溶解。然后滴加16.67克上述制备例4合成 的聚硅氧烷，并在80℃继续搅拌1小时。冷却到40℃以下后，转移到其它容器-20～40℃保存。得到本发明提供的的一种用于太阳能和半导体的材料。
实施例6：
室温下，在大小合适的反应器中依次加入58.55克3-甲氧基-3-甲基丁醇和4.22克聚乙烯醇。加热升温至80℃，然后滴加36.00克水。滴加完成后继续在80℃搅拌直至聚乙烯醇完全溶解。然后添加0.73克三氧化二硼，并在80℃继续搅拌1小时。然后冷却到40℃以下，滴加25克上述制备例4合成的聚硅氧烷。持续搅拌1小时后，转移到其它容器并在-20～40℃保存。得到本发明提供的的一种用于太阳能和半导体的材料。
实施例7：
室温下，在大小合适的反应器中依次加入58.55克3-甲氧基-3-甲基丁醇和4.22克聚乙烯醇。加热升温至80℃，然后滴加36.00克水。滴加完成后继续在80℃搅拌直至聚乙烯醇完全溶解。然后添加0.73克三氧化二硼，并在80℃继续搅拌1小时。然后滴加25克上述制备例6合成的聚硅氧烷。然后加入0.375克三氧化二硼，持续搅拌1小时。冷却至40℃以下，转移到其它容器并在-20～40℃保存。得到本发明提供的的一种用于太阳能和半导体的材料。
实施例8：
室温下，在大小合适的反应器中依次加入58.55克3-甲氧基-3-甲基丁醇和4.22克聚乙烯醇。加热升温至80℃，然后滴加36.00克水。滴加完成后继续在80℃搅拌直至聚乙烯醇完全溶解。然后添加0.73克三氧化二硼，并在80℃继续搅拌1小时。然后滴加25克上述制备例6合成的聚硅氧烷。然后加入0.625克三氧化二硼，持续搅拌1小时。冷却至40℃以下，转移到其它容 器并在-20～40℃保存。得到本发明提供的的一种用于太阳能和半导体的材料。
实施例9：
室温下，在大小合适的反应器中依次加入58.55克3-甲氧基-3-甲基丁醇和4.22克聚乙烯醇。加热升温至80℃，然后滴加36.00克水。滴加完成后继续在80℃搅拌直至聚乙烯醇完全溶解。然后添加0.73克三氧化二硼，并在80℃继续搅拌1小时。然后滴加25克上述制备例1合成的聚硅氧烷。然后依次加入0.625克三氧化二硼和0.2克三乙烯二胺，持续搅拌1小时。冷却至40℃以下，转移到其它容器并在-20～40℃保存。得到本发明提供的的一种用于太阳能和半导体的材料。
实施例10：
室温下，在大小合适的反应器中依次加入58.55克3-甲氧基-3-甲基丁醇和4.22克聚乙烯醇。加热升温至80℃，然后滴加36.00克水。滴加完成后继续在80℃搅拌直至聚乙烯醇完全溶解。然后添加0.73克三氧化二硼，并在80℃继续搅拌1小时。然后冷却到40℃以下，滴加16.67克上述制备例10合成的聚硅氧烷。持续搅拌1小时后，转移到其它容器并在-20～40℃保存。得到本发明提供的的一种用于太阳能和半导体的材料。
实施例11：
室温下，在大小合适的反应器中依次加入58.55克3-甲氧基-3-甲基丁醇和4.22克聚乙烯醇。加热升温至80℃，然后滴加36.00克水。滴加完成后继续在80℃搅拌直至聚乙烯醇完全溶解。然后添加0.73克三氧化二硼，并在80℃继续搅拌1小时。然后滴加16.67克上述制备例10合成的聚硅氧烷。然后加入0.375克三氧化二硼，持续搅拌1小时后，转移到其它容器并在-20～ 40℃保存。得到本发明提供的的一种用于太阳能和半导体的材料。
实施例12：
室温下，在大小合适的反应器中依次加入58.55克3-甲氧基-3-甲基丁醇和4.22克聚乙烯醇。加热升温至80℃，然后滴加36.00克水。滴加完成后继续在80℃搅拌直至聚乙烯醇完全溶解。然后添加0.73克三氧化二硼，并在80℃继续搅拌1小时。然后滴加16.67克上述制备例11合成的聚硅氧烷。然后加入0.75克三氧化二硼，持续搅拌1小时后，转移到其它容器并在-20～40℃保存。得到本发明提供的的一种用于太阳能和半导体的材料。
实施例13：
室温下，在大小合适的反应器中依次加入58.55克3-甲氧基-3-甲基丁醇和4.22克聚乙烯醇。加热升温至80℃，然后滴加36.00克水。滴加完成后继续在80℃搅拌直至聚乙烯醇完全溶解。然后添加0.26克85重量％的磷酸水溶液。然后滴加16.67克上述制备例11合成的聚硅氧烷，并在80℃继续搅拌1小时。冷却到40℃以下后，转移到其它容器-20～40℃保存。得到本发明提供的的一种用于太阳能和半导体的材料。
实施例14：
室温下，在大小合适的反应器中依次加入58.55克3-甲氧基-3-甲基丁醇和4.22克聚乙烯醇。加热升温至80℃，然后滴加36.00克水。滴加完成后继续在80℃搅拌直至聚乙烯醇完全溶解。然后滴加16.67克上述制备例10合成的聚硅氧烷，并在80℃继续搅拌1小时。冷却到40℃以下后，转移到其它容器-20～40℃保存。得到本发明提供的的一种用于太阳能和半导体的材料。
实施例15：
室温下，在大小合适的反应器中依次加入58.55克3-甲氧基-3-甲基丁醇 和4.22克聚乙烯醇。加热升温至80℃，然后滴加36.00克水。滴加完成后继续在80℃搅拌直至聚乙烯醇完全溶解。然后添加0.73克三氧化二硼，并在80℃继续搅拌1小时。然后冷却到40℃以下，滴加25克上述制备例10合成的聚硅氧烷。持续搅拌1小时后，转移到其它容器并在-20～40℃保存。得到本发明提供的的一种用于太阳能和半导体的材料。
实施例16：
室温下，在大小合适的反应器中依次加入58.55克3-甲氧基-3-甲基丁醇和4.22克聚乙烯醇。加热升温至80℃，然后滴加36.00克水。滴加完成后继续在80℃搅拌直至聚乙烯醇完全溶解。然后添加0.73克三氧化二硼，并在80℃继续搅拌1小时。然后滴加25克上述制备例10合成的聚硅氧烷。然后加入0.375克三氧化二硼，持续搅拌1小时。冷却至40℃以下，转移到其它容器并在-20～40℃保存。得到本发明提供的的一种用于太阳能和半导体的材料。
实施例17：
室温下，在大小合适的反应器中依次加入58.55克3-甲氧基-3-甲基丁醇和4.22克聚乙烯醇。加热升温至80℃，然后滴加36.00克水。滴加完成后继续在80℃搅拌直至聚乙烯醇完全溶解。然后添加0.73克三氧化二硼，并在80℃继续搅拌1小时。然后滴加25克上述制备例10合成的聚硅氧烷。然后加入0.625克三氧化二硼，持续搅拌1小时。冷却至40℃以下，转移到其它容器并在-20～40℃保存。得到本发明提供的的一种用于太阳能和半导体的材料。
实施例18：
室温下，在大小合适的反应器中依次加入58.55克3-甲氧基-3-甲基丁醇 和4.22克聚乙烯醇。加热升温至80℃，然后滴加36.00克水。滴加完成后继续在80℃搅拌直至聚乙烯醇完全溶解。然后添加0.73克三氧化二硼，并在80℃继续搅拌1小时。然后滴加25克上述制备例10合成的聚硅氧烷。然后依次加入0.625克三氧化二硼和0.2克三乙烯二胺，持续搅拌1小时。冷却至40℃以下，转移到其它容器并在-20～40℃保存。得到本发明提供的的一种用于太阳能和半导体的材料。
实施例19：
室温下，在大小合适的反应器中依次加入58.55克3-甲氧基-3-甲基丁醇和4.22克聚乙烯醇。加热升温至80℃，然后滴加36.00克水。滴加完成后继续在80℃搅拌直至聚乙烯醇完全溶解。然后添加0.73克三氧化二硼，并在80℃继续搅拌1小时。然后冷却到40℃以下，滴加20克上述制备例10合成的聚硅氧烷。持续搅拌1小时后，转移到其它容器并在-20～40℃保存。得到本发明提供的的一种用于太阳能和半导体的材料。
实施例20：
室温下，在大小合适的反应器中依次加入58.55克3-甲氧基-3-甲基丁醇和4.22克聚乙烯醇。加热升温至80℃，然后滴加36.00克水。滴加完成后继续在80℃搅拌直至聚乙烯醇完全溶解。然后添加0.73克三氧化二硼，并在80℃继续搅拌1小时。然后冷却到40℃以下，滴加16克上述制备例13合成的聚硅氧烷。持续搅拌1小时后，转移到其它容器并在-20～40℃保存。得到本发明提供的的一种用于太阳能和半导体的材料。
实施例21：
室温下，在大小合适的反应器中依次加入58.55克3-甲氧基-3-甲基丁醇和4.22克聚乙烯醇。加热升温至80℃，然后滴加36.00克水。滴加完成后继 续在80℃搅拌直至聚乙烯醇完全溶解。然后添加0.73克三氧化二硼，并在80℃继续搅拌1小时。然后冷却到40℃以下，滴加9克上述制备例14合成的聚硅氧烷。持续搅拌1小时后，转移到其它容器并在-20～40℃保存。得到本发明提供的的一种用于太阳能和半导体的材料。
实施例22：
室温下，在大小合适的反应器中依次加入58.55克3-甲氧基-3-甲基丁醇和4.22克聚乙烯醇。加热升温至80℃，然后滴加36.00克水。滴加完成后继续在80℃搅拌直至聚乙烯醇完全溶解。然后添加0.73克三氧化二硼，并在80℃继续搅拌1小时。然后冷却到40℃以下，滴加17克上述制备例15合成的聚硅氧烷。持续搅拌1小时后，转移到其它容器并在-20～40℃保存。得到本发明提供的的一种用于太阳能和半导体的材料。
实施例23：
室温下，在大小合适的反应器中依次加入58.55克3-甲氧基-3-甲基丁醇和4.22克聚乙烯醇。加热升温至80℃，然后滴加36.00克水。滴加完成后继续在80℃搅拌直至聚乙烯醇完全溶解。然后添加0.73克三氧化二硼，并在80℃继续搅拌1小时。然后冷却到40℃以下，滴加16.4克上述制备例16合成的聚硅氧烷。持续搅拌1小时后，转移到其它容器并在-20～40℃保存。得到本发明提供的的一种用于太阳能和半导体的材料。
实施例24：
室温下，在大小合适的反应器中依次加入58.55克3-甲氧基-3-甲基丁醇和4.22克聚乙烯醇。加热升温至80℃，然后滴加36.00克水。滴加完成后继续在80℃搅拌直至聚乙烯醇完全溶解。然后添加0.73克三氧化二硼，并在80℃继续搅拌1小时。然后冷却到40℃以下，滴加6克上述制备例17合成 的聚硅氧烷。持续搅拌1小时后，转移到其它容器并在-20～40℃保存。得到本发明提供的的一种用于太阳能和半导体的材料。
实施例25：
室温下，在大小合适的反应器中依次加入58.55克3-甲氧基-3-甲基丁醇和4.22克聚乙烯醇。加热升温至80℃，然后滴加36.00克水。滴加完成后继续在80℃搅拌直至聚乙烯醇完全溶解。然后添加0.73克三氧化二硼，并在80℃继续搅拌1小时。然后冷却到40℃以下，滴加19克上述制备例18合成的聚硅氧烷。持续搅拌1小时后，转移到其它容器并在-20～40℃保存。得到本发明提供的的一种用于太阳能和半导体的材料。
实施例26：
室温下，在大小合适的反应器中依次加入58.55克3-甲氧基-3-甲基丁醇和4.22克聚乙烯醇。加热升温至80℃，然后滴加36.00克水。滴加完成后继续在80℃搅拌直至聚乙烯醇完全溶解。然后添加0.73克三氧化二硼，并在80℃继续搅拌1小时。然后冷却到40℃以下，滴加18.3克上述制备例19合成的聚硅氧烷。持续搅拌1小时后，转移到其它容器并在-20～40℃保存。得到本发明提供的的一种用于太阳能和半导体的材料。
对比例1：
室温下，在大小合适的反应器中依次加入58.55克3-甲氧基-3-甲基丁醇和4.22克聚乙烯醇。加热升温至80℃，然后滴加36.00克水。滴加完成后继续在80℃搅拌直至聚乙烯醇完全溶解。然后添加0.73克三氧化二硼，并在80℃继续搅拌1小时。冷却至40℃以下，转移到其它容器并在-20～40℃保存。得到掺杂浆料。
对比例2：
室温下，在大小合适的反应器中依次加入58.55克3-甲氧基-3-甲基丁醇和4.22克聚乙烯醇。加热升温至80℃，然后滴加36.00克水。滴加完成后继续在80℃搅拌直至聚乙烯醇完全溶解。然后添加0.73克三氧化二硼，并在80℃继续搅拌1小时。然后滴加重均分子量4400克/摩尔的聚二甲基硅氧烷40质量％二乙二醇单甲醚溶液16.67克。持续搅拌1小时。冷却至40℃以下，有油状物析出。得到掺杂浆料均匀性不足。
对比例3：
室温下，在大小合适的反应器中依次加入58.55克3-甲氧基-3-甲基丁醇和4.22克聚乙烯醇。加热升温至80℃，然后滴加36.00克水。滴加完成后继续在80℃搅拌直至聚乙烯醇完全溶解。然后添加0.73克三氧化二硼，并在80℃继续搅拌1小时。然后滴加重均分子量5000克/摩尔的聚苯基硅氧烷40质量％二乙二醇单甲醚溶液16.67克。持续搅拌1小时。冷却至40℃以下，有油状物析出。得到掺杂浆料均匀性不足。
《掺杂浆料以及掩膜材料的性能评测》
根据实施例1～26以及对比例1～3所制备的掺杂浆料及掩膜材料，分别使用旋转涂布条件涂布在6英寸N型单晶硅片上，然后进行热扩散来评测相关性能。旋涂条件分别为：(A)转速1000rpm持续10秒、(B)转速1500rpm持续10秒、(C)转速2000rpm持续10秒。硅片A：半导体用单面抛光，CZ直拉法掺磷N型单晶硅片，晶向100，电阻率0.5-6Ω.cm，厚度625微米。硅片B：太阳能电池用双面制绒，CZ直拉法掺磷N型单晶硅片，晶向100，电阻率1-7Ω.cm，厚度180微米。阻隔性评价时硅片放置方式如说明书附图1，气中扩散性评价时硅片放置方式如说明书附图2。电阻测试仪：日本NAPSON四探针电阻率测试仪，手动版RT-70V/RG-7。性能测评结果如下：
表1
Figure PCTCN2017098627-appb-000037
表2
Figure PCTCN2017098627-appb-000038
Figure PCTCN2017098627-appb-000039
从上述表1和表2中的测评结果可以发现，与对比例1的性能相比，添加了本发明所提供的聚硅氧烷的掺杂浆料以及掩膜材料在保持同等程度的扩散性的基础上，阻隔性和对气中扩散的抑制均得到了大幅度的提高。
实际应用包含但并不仅限于：上述实施例所述的聚合物结构、分子量，掺杂浆料的组成成分、含量，适用的半导体基材，涂布的条件，扩散条件等。
实施例27：
首先，在两面的表面上实施了绒面加工的n型半导体基板的一面上，用旋涂机在整个面上涂布p型杂质扩散组合物，150摄氏度干燥1分钟，制作了一面上形成了p型杂质扩散组合物膜的半导体基板。
接着，如图3(ii)所示，扩散舟内，设置了一面上形成了p型杂质扩散组合物膜的半导体基板。两片一组的半导体基板的各自的形成了p型杂质扩散组合物膜的面间的距离以及未形成p型杂质扩散组合物膜的面间的距离各 为3mm。
然后，向流入O2：0.2L/min、N2：9.8L/min的扩散炉(光洋热处理株式会社、206A-M100)中，在设定为700摄氏度的状态下，导入扩散舟。之后，以15摄氏度/min的速度升温至950摄氏度，在950摄氏度热处理30分钟形成p型杂质扩散层。
然后，以10摄氏度/min的速度降温至830摄氏度。在830摄氏度，将O2：0.2L/min、N2：9.8L/min、以及在POCl3中鼓泡后的N2：1.5L/min流入扩散炉中处理5分钟。之后，停止在POCl3中鼓泡的氮气流，在O2：0.2L/min、N2：9.8L/min的流入气体中，同样温度下热处理12分钟，在形成了p型杂质扩散组合物膜的领域外的位置处形成了n型杂质扩散层。之后，以10摄氏度/min的速度降温至700摄氏度，从扩散炉中取出n型半导体基板。
接下来，使用氢氟酸除去n型半导体基板的表面上残存的玻璃层(p型杂质扩散组合物的人处理物10以及磷硅玻璃层11)。P型杂质扩散层领域的方块电阻的平均值为65Ω/□，p型杂质扩散组合物膜形成的面的反面上形成的n型杂质扩散层区域的方块电阻的平均值为55Ω/□。
(p型杂质扩散层形成时的向外扩散的评价)
通过实施例27制作的半导体基板的n型杂质扩散层中，n型半导体基板表层的硼元素浓度用SIMS(二次离子质谱分析仪，Cameca公司、IMS-7F)来测定。一次离子使用了Cs+。N型半导体基板表层的硼浓度为在7*1017个原子/cm3以下，抑制了向n型半导体基板表层上的硼污染。
实施例28：
在两面的表面上实施了制绒加工的n型半导体基板的一面上，使用旋转涂布在整个面上涂布与实施例18一样的p型杂质扩散组合物，150摄氏度下 干燥1分钟，制作了一面上形成了p型杂质扩散组合物膜的半导体基板。
接着，如图3所示在扩散舟中设置一面上形成了p型杂质扩散组合物膜的半导体基板。两片一组的半导体基板的各自的形成了p型杂质扩散组合物膜的面间的距离为0mm，未形成p型杂质扩散组合物膜的面间的距离为3mm。
然后，流入O2：0.2L/min、N2：9.8L/min的扩散炉(光洋热处理株式会社、206A-M100)中，在设定为700摄氏度的状态下，导入扩散舟。之后，以15摄氏度/min的速度升温至950摄氏度，在950摄氏度热处理30分钟形成p型杂质扩散层。
然后，以10摄氏度/min的速度降温至830摄氏度。在830摄氏度，将O2：0.2L/min、N2：9.8L/min、以及在POCl3中鼓泡后的N2：1.5L/min流入扩散炉中处理5分钟。之后，停止在POCl3中鼓泡的氮气流，在O2：0.2L/min、N2：9.8L/min的流入气体中，同样温度下热处理12分钟，在形成了p型杂质扩散组合物膜的区域外的位置处形成了n型杂质扩散层。之后，以10摄氏度/min的速度降温至700摄氏度，从扩散炉中取出n型半导体基板。
接下来，使用氢氟酸除去n型半导体基板的表面上残存的玻璃层(p型杂质扩散组合物的人处理物10以及磷硅玻璃层11)。P型杂质扩散层区域的方块电阻的平均值为67Ω/□，p型杂质扩散组合物膜形成的面的反面上形成的n型杂质扩散层区域的方块电阻的平均值为56Ω/□。
(p型杂质扩散层形成时的向外扩散的评价)
通过实施例28制作的半导体基板的n型杂质扩散层中，n型半导体基板表层的硼元素浓度用SIMS(二次离子质谱分析仪，Cameca公司、IMS-7F)来测定。一次离子使用了Cs+。N型半导体基板表层的硼浓度为在6*1016个原子/cm3以下，抑制了向n型半导体基板表层上的硼污染。
实施例29：
在两面的表面上实施了制绒加工的n型半导体基板的一面上，使用旋转涂布在整个面上涂布与实施例18一样的p型杂质扩散组合物，150摄氏度下干燥1分钟，制作了一面上形成了p型杂质扩散组合物膜的半导体基板。
接着，如图3所示在扩散舟中设置一面上形成了p型杂质扩散组合物膜的半导体基板。两片一组的半导体基板的各自的形成了p型杂质扩散组合物膜的面间的距离为0mm，未形成p型杂质扩散组合物膜的面间的距离为3mm。
然后，向流入O2：0.2L/min、N2：9.8L/min的扩散炉(光洋热处理株式会社、206A-M100)中，在设定为700摄氏度的状态下，导入扩散舟。之后，以15摄氏度/min的速度升温至950摄氏度，在950摄氏度热处理30分钟形成p型杂质扩散层。
然后，以10摄氏度/min的速度降温至830摄氏度。在830摄氏度，将O2：0.2L/min、N2：9.8L/min、以及在POCl3中鼓泡后的N2：1.5L/min流入扩散炉中处理5分钟。之后，停止在POCl3中鼓泡的氮气流，在O2：0.2L/min、N2：9.8L/min的流入气体中，同样温度下热处理12分钟，在形成了p型杂质扩散组合物膜的区域外的位置处形成了n型杂质扩散层。之后，以10摄氏度/min的速度降温至700摄氏度，从扩散炉中取出n型半导体基板。
之后，以10摄氏度/min的速度升温至900摄氏度，在900摄氏度，O2：5L/min的气流中，同样温度下热处理20分钟，将半导体基板的表面氧化。
之后，以10摄氏度/min的速度降温至700摄氏度，从扩散炉中取出n型半导体基板。
接下来，使用氢氟酸除去n型半导体基板的表面上残存的玻璃层(p型杂质扩散组合物的人处理物10以及磷硅玻璃层11)。p型杂质扩散层区域的 方块电阻的平均值为60Ω/□，p型杂质扩散组合物膜形成的面的反面上形成的n型杂质扩散层区域的方块电阻的平均值为51Ω/□。
(p型杂质扩散层形成时的向外扩散的评价)
通过实施例29制作的半导体基板的n型杂质扩散层中，n型半导体基板表层的硼元素浓度用SIMS(二次离子质谱分析仪，Cameca公司、IMS-7F)来测定。一次离子使用了Cs+。N型半导体基板表层的硼浓度为在5*1015个原子/cm3以下，抑制了向n型半导体基板表层上的硼污染。
实施例30：
在两面的表面上实施了制绒加工的n型半导体基板的一面上，使用旋转涂布在整个面上涂布与实施例18一样的p型杂质扩散组合物，150摄氏度下干燥1分钟，制作了一面上形成了p型杂质扩散组合物膜的半导体基板。
接着，如图3所示，在扩散舟中设置一面上形成了p型杂质扩散组合物膜的半导体基板。两片一组的半导体基板的各自的形成了p型杂质扩散组合物膜的面间的距离为0mm，未形成p型杂质扩散组合物膜的面间的距离为3mm。
然后，向流入O2：0.2L/min、N2：9.8L/min的扩散炉(光洋热处理株式会社、206A-M100)中，在设定为700摄氏度的状态下，导入扩散舟。之后，以15摄氏度/min的速度升温至950摄氏度，在950摄氏度热处理30分钟形成p型杂质扩散层。
之后，以10摄氏度/min的速度降温至900摄氏度。在900摄氏度，O2：5L/min的气流中，同样温度下热处理20分钟，将半导体基板的表面氧化。
然后，以10摄氏度/min的速度降温至830摄氏度。在830摄氏度，O2：0.2L/min、N2：9.8L/min、以及在POCl3中鼓泡后的N2：1.5L/min流入扩散 炉中处理5分钟。之后，停止在POCl3中鼓泡的氮气流，在O2：0.2L/min、N2：9.8L/min的流入气体中，同样温度下热处理12分钟，形成了p型杂质扩散组合物膜的区域外的位置处形成了n型杂质扩散层。之后，以10摄氏度/min的速度降温至700摄氏度，从扩散炉中取出n型半导体基板。
接下来，使用氢氟酸除去n型半导体基板的表面上残存的玻璃层(p型杂质扩散组合物的人处理物10以及磷硅玻璃层11)。p型杂质扩散层区域的方块电阻的平均值为62Ω/□，p型杂质扩散组合物膜形成的面的反面上形成了的n型杂质扩散层区域的方块电阻的平均值为61Ω/□。
(p型杂质扩散层形成时的向外扩散的评价)
通过实施例30制作的半导体基板的n型杂质扩散层中，n型半导体基板表层的硼元素浓度用SIMS(二次离子质谱分析仪，Cameca公司、IMS-7F)来测定。一次离子使用了Cs+。N型半导体基板表层的硼浓度为在2*1016个原子/cm3以下，抑制了向n型半导体基板表层上的硼污染。
实施例31：
在两面的表面上实施了制绒加工的n型半导体基板的一面上，使用旋转涂布在整个面上涂布与实施例18一样的p型杂质扩散组合物，150摄氏度下干燥1分钟，制作了一面上形成了p型杂质扩散组合物膜的半导体基板。
接着，如图3所示，在扩散舟中设置一面上形成了p型杂质扩散组合物膜的半导体基板。两片一组的半导体基板的各自的形成了p型杂质扩散组合物膜的面间的距离为0mm，未形成p型杂质扩散组合物膜的面间的距离为3mm。
然后，向流入O2：0.2L/min、N2：9.8L/min的扩散炉(光洋热处理株式会社、206A-M100)中，在设定为700摄氏度的状态下，导入扩散舟。
之后，以15摄氏度/min的速度升温至900摄氏度，在900摄氏度，O2：5L/min的气流中，同样温度下热处理20分钟，将半导体基板的表面氧化。
之后，以15摄氏度/min的速度升温至950摄氏度，在950摄氏度热处理30分钟形成p型杂质扩散层。
然后，以10摄氏度/min的速度降温至830摄氏度。在830摄氏度，将O2：0.2L/min、N2：9.8L/min、以及在POCl3中鼓泡后的N2：1.5L/min流入扩散炉中处理5分钟。之后，停止在POCl3中鼓泡的氮气流，在O2：0.2L/min、N2：9.8L/min的流入气体中，同样温度下热处理12分钟，在形成了p型杂质扩散组合物膜的区域外的位置处形成了n型杂质扩散层。之后，以10摄氏度/min的速度降温至700摄氏度，从扩散炉中取出n型半导体基板。
接下来，使用氢氟酸除去n型半导体基板的表面上残存的玻璃层(p型杂质扩散组合物的热处理物10以及磷硅玻璃层11)。p型杂质扩散层区域的方块电阻的平均值为64Ω/□，p型杂质扩散组合物膜形成的面的反面上形成的n型杂质扩散层区域的方块电阻的平均值为65Ω/□。
(p型杂质扩散层形成时的向外扩散的评价)
通过实施例31制作的半导体基板的n型杂质扩散层中，n型半导体基板表层的硼元素浓度用SIMS(二次离子质谱分析仪，Cameca公司、IMS-7F)来测定。一次离子使用了Cs+。N型半导体基板表层的硼浓度为在4*1016个原子/cm3以下，抑制了向n型半导体基板表层上的硼污染。
对比例4：
在两面的表面上实施了制绒加工的n型半导体基板的一面上使用旋转涂布在整个面上涂布与实施例18一样的p型杂质扩散组合物，150摄氏度下干燥1分钟，制作了一面上形成了p型杂质扩散组合物膜的半导体基板。
接着，如图6所示，将各自的形成了p型杂质扩散组合物膜的面朝一个方向，在扩散舟中设置一面上形成了p型杂质扩散组合物膜的半导体基板。各半导体基板的距离全都为3mm。
然后，向流入O2：0.2L/min、N2：9.8L/min的扩散炉(光洋热处理株式会社、206A-M100)中，设定为700摄氏度的状态下，导入扩散舟。之后，以15摄氏度/min的速度升温至950摄氏度，在950摄氏度热处理30分钟形成p型杂质扩散层。
然后，以10摄氏度/min的速度降温至830摄氏度。在830摄氏度，O2：0.2L/min、N2：9.8L/min、以及在POCl3中鼓泡后的N2：1.5L/min流入扩散炉中处理5分钟。之后，停止在POCl3中鼓泡的氮气流，在O2：0.2L/min、N2：9.8L/min的流入气体中，同样温度下热处理12分钟，在形成了p型杂质扩散组合物膜的区域外的位置处形成了n型杂质扩散层。之后，以10摄氏度/min的速度降温至700摄氏度，从扩散炉中取出n型半导体基板。
接下来，使用氢氟酸除去n型半导体基板的表面上残存的玻璃层(p型杂质扩散组合物的人处理物10以及磷硅玻璃层11)。P型杂质扩散层区域的方块电阻的平均值为66Ω/□，p型杂质扩散组合物膜形成的面的反面上形成了的n型杂质扩散层区域的方块电阻的平均值为56Ω/□。
(p型杂质扩散层形成时的向外扩散的评价)
通过对比例4制作的半导体基板的n型杂质扩散层中，n型半导体基板表层的硼元素浓度用SIMS(二次离子质谱分析仪，Cameca公司、IMS-7F)来测定。一次离子使用了Cs+。N型半导体基板表层的硼浓度为在1*1020个原子/cm3以下，在n型半导体基板表层上发生硼污染。
从上述评价结果可以发现，与对比例4的性能相比，本发明所述的半导 体单元的制造方法可以非常有效地抑制硼向外扩散，特别是大大降低了对n型基板表面上的污染。
《工业上的可利用性》
本发明所提供的聚硅氧烷可以用于掺杂浆料、掩膜材料、半导体(包含太阳能电池)中。

Claims (38)

  1. 一种聚硅氧烷，其特征在于：含有至少一种选自下式1所示的分子结构片段，
    Figure PCTCN2017098627-appb-100001
    式1中，Q为含有醇羟基且主链碳原子数小于12的烷基或者含有醇羟基且主链非氢原子数小于12且含杂原子的烷基；T为羟基、烷基、含有醇羟基且主链碳原子数小于12的烷基或者含有醇羟基且主链非氢原子数小于12且含杂原子的烷基。
  2. 根据权利要求1所述的聚硅氧烷，其特征在于：所述Q为式2所示的结构片段，
    Figure PCTCN2017098627-appb-100002
    式2中，X为碳原子数小于7的烷基或者主链非氢原子数小于7且含杂原子的烷基；R1、R2、R3分别独立为氢原子、碳原子数小于3的取代基，或者R2与X上的碳原子连接成为环状取代基。
  3. 根据权利要求2所述的聚硅氧烷，其特征在于：所述X为主链非氢原子数小于7且含杂原子的烷基。
  4. 根据权利要求2所述的聚硅氧烷，其特征在于：所述R1、R2、R3分别独立为氢原子、碳原子数为1的取代基或者R2与X上的碳原子连接成为环状取代基。
  5. 根据权利要求2～4中任意一项所述的聚硅氧烷，其特征在于：所述R1、 R2、R3分别独立为氢原子。
  6. 根据权利要求1～5中任意一项所述的聚硅氧烷，其特征在于：所述聚硅氧烷仅由Q为式2所示的分子结构片段构成的式1所示的分子结构片段组成。
  7. 根据权利要求6所述的聚硅氧烷，其特征在于：所述分子结构片段为相同的分子结构片段。
  8. 根据权利要求1～5中任意一项所述的聚硅氧烷，其特征在于：还含有摩尔含量1～99％的至少一种选自下式3所示的分子结构片段，
    Figure PCTCN2017098627-appb-100003
    式3中X1为碳原子数小于8的烷基或碳原子数小于10的芳基；Y1为羟基、碳原子数小于10的芳基或者碳原子数小于8的烷基。
  9. 根据权利要求8所述的聚硅氧烷，其特征在于：所述式3所示的分子结构片段的摩尔含量为1～50％。
  10. 根据权利要求8～9中任意一项所述的聚硅氧烷，其特征在于：所述Y1为羟基。
  11. 根据权利要求1～10中任意一项所述的聚硅氧烷，其特征在于：T为羟基、碳原子数小于8的烷基或者含有式4所示的结构，
    Figure PCTCN2017098627-appb-100004
    式4中Z为碳原子数小于7的烷基或者主链非氢原子数小于7且含杂原子的的烷基；R4、R5、R6分别独立为氢原子、碳原子数小于3的取代基，或者R5与Z上的碳原子连接成为环状取代基。
  12. 根据权利要求11所述的聚硅氧烷，其特征在于：所述Z为主链非氢原子数小于7且含杂原子的烷基。
  13. 根据权利要求1～12中任意一项所述的聚硅氧烷，其特征在于：所述T为羟基。
  14. 根据权利要求1～13中任意一项所述的聚硅氧烷，其特征在于：所述聚硅氧烷不含有环氧乙烷结构。
  15. 根据权利要求1～14中任意一项所述的聚硅氧烷，其特征在于：所述聚硅氧烷的重均分子量为500～50000。
  16. 根据权利要求15所述的聚硅氧烷，其特征在于：所述聚硅氧烷的重均分子量为1000～11000。
  17. 根据权利要求16所述的聚硅氧烷，其特征在于：所述聚硅氧烷的重均分子量为1500～5500。
  18. 一种用于太阳能和半导体的材料，其特征在于：含有权利要求1～17任意一项所述的聚硅氧烷。
  19. 根据权利要求18所述的用于太阳能和半导体的材料，其特征在于还含有：
    掺杂剂成分A、
    高分子粘结剂B、和
    溶剂C。
  20. 根据权利要求19所述的用于太阳能和半导体的材料，其特征在于：所述掺杂剂成分A为包含第5主族元素的化合物的n型掺杂剂成分、或者为包含第3主族元素的化合物的p型掺杂剂成分。
  21. 根据权利要求20所述的用于太阳能和半导体的材料，其特征在于：所 述掺杂剂成分A包含无机硼化合物成分或者无机磷化合物成分。
  22. 根据权利要求19所述的用于太阳能和半导体的材料，其特征在于：所述高分子粘结剂B的分子结构重复单元中包含醇羟基。
  23. 根据权利要求22所述的用于太阳能和半导体的材料，其特征在于：所述高分子粘结剂B的重均分子量范围为1000～300000。
  24. 根据权利要求19所述的用于太阳能和半导体的材料，其特征在于：所述溶剂C由0～50％的水以及50～100％有机溶剂组成。
  25. 根据权利要求24所述的用于太阳能和半导体的材料，其特征在于：所述有机溶剂C为沸点50～300摄氏度的有机溶剂。
  26. 根据权利要求19所述的用于太阳能和半导体的材料，其特征在于：所述掺杂剂成分A、高分子粘结剂B、聚硅氧烷和溶剂C的总添加量相对于浆料的总质量为2～30％。
  27. 一种半导体基板的半导体单元的制造方法，其特征在于：所述方法含有如下a～c的工序，
    a.将权利要求19-26中任一项中所述的材料作为第一导电型杂质扩散组合物涂布在各半导体基板的一面，形成第一导电型杂质扩散组合物膜，
    b.对a工序制备得到的形成有所述第一导电型杂质扩散组合物膜的半导体基板进行加热，使所述材料中的掺杂剂成分A中所含的第一导电型杂质向所述半导体基板中扩散，形成第一导电型杂质扩散层，
    c.在含有第二导电型杂质的气体的气氛下加热所述半导体基板，使第二导电型的杂质向所述半导体基板中扩散，形成第二导电型杂质扩散层，
    其中，在工序b以及c中，把两片一组的所述半导体基板的各自形成了第一导电型的杂质扩散组合物膜的面相向放置。
  28. 根据权利要求27所述的半导体单元的制造方法，其特征在于：所述c工序是在所述b工序后，将所述第一导电型杂质扩散组合物膜的热处理物作为掩膜来进行。
  29. 根据权利要求27所述的半导体单元的制造方法，其特征在于：所述c工序在所述b工序之后连续于所述b工序而进行。
  30. 根据权利要求27所述的半导体单元制造方法，其特征在于：所述c工序中，第二导电型杂质扩散层形成时的加热温度与所述b工序中第一导电型杂质扩散层形成时的温度相比低50～200℃。
  31. 根据权利要求27所述的半导体单元制造方法，其特征在于：还含有d工序：在含有氧气的气氛下使半导体基板表面氧化。
  32. 根据权利要求31所述的半导体单元制造方法，其特征在于：所述d工序在所述c工序之后连续于所述c工序而进行。
  33. 根据权利要求27所述的半导体单元制造方法，其特征在于：在所述b以及c工序中，对所述两片一组的半导体基板的多个组而言，以各组中所述第一导电型的杂质扩散组合物膜形成的面之间的距离为W1，以相邻两组间所述第一导电型的杂质扩散组合物膜形成面的反面之间的距离为W2，W1和W2满足W1＜W2。
  34. 根据权利要求33所述的半导体单元制造方法，其特征在于：所述b以及c工序中多片半导体基板的配置中，所述两片一组的半导体基板的所述第一导电型的杂质扩散组合物膜形成的面之间的距离为0mm。
  35. 根据权利要求27所述的半导体单元制造方法，其特征在于：所述b工序为在含有氧气的气氛下进行。
  36. 根据权利要求35所述的半导体单元制造方法，其特征在于：所述b工 序中气氛中的氮气与氧气的比例与所述c工序中的气氛中氮气与氧气比例相同。
  37. 根据权利要求27所述的半导体单元制造方法，其特征在于：所述第一导电型为p型，所述第二导电型为n型。
  38. 一种根据权利要求27～37中任意一项所述的半导体单元制造方法制备的太阳能电池。
PCT/CN2017/098627 2016-08-31 2017-08-23 聚硅氧烷、半导体用材料、半导体及太阳能电池制备方法 Ceased WO2018040990A1 (zh)

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