CN108475014B - Photosensitive resin composition and method for manufacturing semiconductor device - Google Patents

Photosensitive resin composition and method for manufacturing semiconductor device Download PDF

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CN108475014B
CN108475014B CN201680076774.XA CN201680076774A CN108475014B CN 108475014 B CN108475014 B CN 108475014B CN 201680076774 A CN201680076774 A CN 201680076774A CN 108475014 B CN108475014 B CN 108475014B
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photosensitive resin
ion implantation
resin composition
film
substrate
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CN108475014A (en
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添田淳史
池田吉纪
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Teijin Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02524—Group 14 semiconducting materials
    • H01L21/02529—Silicon carbide
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/26—Bombardment with radiation
    • H01L21/263—Bombardment with radiation with high-energy radiation
    • H01L21/265—Bombardment with radiation with high-energy radiation producing ion implantation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/26—Bombardment with radiation
    • H01L21/263—Bombardment with radiation with high-energy radiation
    • H01L21/265—Bombardment with radiation with high-energy radiation producing ion implantation
    • H01L21/266—Bombardment with radiation with high-energy radiation producing ion implantation using masks

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Health & Medical Sciences (AREA)
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  • Ceramic Engineering (AREA)
  • Chemical & Material Sciences (AREA)
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  • Materials For Photolithography (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)

Abstract

Provided are a photosensitive resin composition which has high-temperature heat resistance and conductivity, does not cause a risk of generation of metal impurities in a semiconductor substrate, can be subjected to pattern formation, and can be applied to a high-temperature ion implantation process at low cost, and a method for manufacturing a semiconductor device using the same. The photosensitive resin composition of the present invention contains a photosensitive resin and particles of a conductive material and/or a semiconductor material. Further, the method of the present invention of manufacturing a semiconductor device includes: a step of forming a pattern (11) of a film of the photosensitive resin composition of the present invention on a semiconductor layer or a substrate (2); a step of forming an ion implantation mask (13) by baking a pattern of a film of a photosensitive resin composition; implanting ions into the semiconductor layer or the substrate (2) through the pattern opening (12) of the ion implantation mask; and a step of removing the ion implantation mask (13).

Description

Photosensitive resin composition and method for manufacturing semiconductor device
Technical Field
The present invention relates to a photosensitive resin composition and a method for manufacturing a semiconductor device using the same.
Background
Most of the present power semiconductor devices are manufactured using semiconductor Si. In a power semiconductor device using Si, the performance limit due to the material properties of Si is close. SiC, which is a semiconductor material, has voltage-resistant characteristics greatly exceeding those of semiconductor Si, high saturated electron mobility, and high thermal conductivity. Therefore, the semiconductor device is promising as a power semiconductor material in the next generation because the system can be miniaturized by improving the performance of the power semiconductor device, reducing the loss, and simplifying the device cooling mechanism.
In order to manufacture a SiC power device, it is necessary to implant ions and dope carriers into a desired portion in SiC. In ion doping of SiC, since the diffusion coefficient of a dopant of SiC is small and it is difficult to apply a thermal diffusion method, a doping method by ion implantation is widely used.
In the step of lowering the resistance of SiC by ion implantation, it is necessary to perform ion implantation at a high dose. However, if ion implantation is performed at a high concentration at room temperature, SiC is amorphized, and the desired device performance cannot be obtained. Further, SiC that is temporarily amorphized is difficult to recover to the same polycrystalline structure having the same crystallinity as before ion implantation even by thermal calcination or the like.
Therefore, a high-temperature ion implantation method is known in which, in an ion implantation step into SiC, the crystallinity of the base material is restored simultaneously with the ion implantation by maintaining the base material at a high temperature of 200 ℃.
In the above-described high-temperature ion implantation method, since ion implantation is performed at a high temperature of 200 ℃ or higher, a photoresist material used for ion implantation of silicon at room temperature, for example, a chemically amplified photoresist, cannot be used as an ion implantation mask layer.
Therefore, in the above-mentioned high-temperature ion implantation method, it is proposed to use SiO having sufficient heat resistance at the substrate temperature in the ion implantation step as an ion implantation mask2Etc. inorganic membranes, e.g. by chemistrySiO deposited by Vapor deposition (CVD: Chemical Vapor Transport (CVD)) or the like2And the like (for example, patent document 1). By patterning the semiconductor SiC in advance with such a heat-resistant ion implantation mask, carrier doping can be performed in a desired region in the semiconductor SiC through the opening of the ion implantation mask.
In the patterning of such a heat-resistant ion implantation mask, a dry process such as a wet etching method or a Reactive Ion Etching (RIE) method using a photoresist as a mask is used.
An example of the ion implantation mask forming step and the ion implantation step will be described with reference to fig. 2.
First, a SiC substrate (2) having a SiC epitaxial growth film (1) is provided (fig. 2(a)), and SiO is deposited on the SiC epitaxial growth film (1) by a CVD method or the like2Membrane (3) (fig. 2 (b)). Then, in SiO2On the film (3), a photosensitive resist (4) is formed (fig. 2 (c)). Thereafter, patterning exposure and development, which are general photolithography steps, are performed to pattern a photosensitive resist (fig. 2 (d)). Thereafter, SiO is performed by hydrofluoric acid or the like2Removing the film to obtain a desired SiO having mask pattern openings (12)2Film pattern (fig. 2 (e)). Then, passing through O2Ashing is performed to remove the photosensitive resist (fig. 2 (f)). Thereafter, ion implantation is performed at a high temperature of 200 ℃ or higher using a beam (7) of dopant ions to form an ion implanted region (6) (fig. 2(g)), and SiO is stripped by a wet process using hydrofluoric acid or the like2Membrane (fig. 2 (h)).
The ion implantation process requires a simplified process because it has a large number of steps and is a complicated and expensive process.
In order to simplify the process, a method of performing ion implantation at room temperature using a chemically amplified resist as an ion implantation mask has been proposed (for example, patent document 2).
As in patent documents 1 and 2, when high-density ion implantation is performed on a semiconductor covered with an insulator film such as an ion implantation mask, charging (charge-up) that occurs in the substrate and the insulator film becomes a problem. Ion implantationIn the step, if the substrate and the insulator film are charged, a potential difference may be generated between the semiconductor substrate and the insulator such as an ion implantation mask and a region where ion implantation is performed in the semiconductor, and a discharge phenomenon may occur. Further, the density of the implanted ions may be made non-uniform due to a spatial electric field generated by the charging. It is known that for these reasons, when high-density ion implantation is performed on a semiconductor covered with an insulator film, performance and yield of the semiconductor device are reduced. The charging phenomenon is particularly caused by SiO on the surface of the semiconductor2The first case of insulator film coverage is remarkable.
In order to solve the above-described problem of charging, a means has been proposed in which a low-energy secondary ion shower having a polarity opposite to that of the implanted ions is supplied to the surface of the substrate to neutralize the charging of the substrate (for example, patent document 3).
As a means for solving the above-mentioned problem of charging, in addition to a means using an ion shower, a technique using the following means is proposed: in ion implantation, an insulating ion implantation mask is covered with a conductive antistatic film such as a metal film or a doped semiconductor film in advance (for example, patent document 4).
In addition, for the purpose of improving an ion implantation mask as an ion blocking layer, a means of using a thin metal film of titanium, molybdenum, or the like having a high density and high ion shielding performance as an ion implantation mask has been proposed (for example, patent document 5).
As a means for omitting the process of forming the ion implantation mask layer, a process using a siloxane-containing photoresist is known (for example, patent document 6).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2006-324585
Patent document 2: japanese laid-open patent publication No. 2008-108869
Patent document 3: japanese laid-open patent publication No. 6-295700
Patent document 4: japanese laid-open patent publication No. 7-58053
Patent document 5: japanese patent laid-open publication No. 2007-42803
Patent document 6: international publication No. 2013/099785.
Disclosure of Invention
Problems to be solved by the invention
Patent document 1 describes that SiO is grown by CVD method2The film is used as an ion implantation mask. In this means, SiO2The film is excellent in heat resistance and thus can be ion-implanted at high temperature, but SiO2Patterning of the film requires a complicated process and is costly. Further, as described above, SiO as an ion implantation mask2Since the film does not have conductivity, there is a problem that charging occurs in a high-density ion implantation step.
Patent document 2 describes a means for using a chemically amplified resist as an ion implantation mask. This method is low cost because of simple process, but has a problem that it cannot be applied to a high temperature ion implantation process because of low heat resistance of a chemically amplified resist. Further, as described above, since the chemically amplified resist has no conductivity, there is a problem that charging occurs in a high-density ion implantation step.
Patent document 3 describes a means for solving the problem of charging using an ion shower. This method requires an ion shower apparatus to be installed in a semiconductor device manufacturing apparatus, and therefore has a problem of high cost. Further, it is difficult to control the amount of ion shower supply, and it is difficult to neutralize the charge generated on the surface of the substrate without excess or shortage, and it is difficult to completely solve the problem of the charge.
Patent document 4 describes a means for covering an insulating ion implantation mask with a conductive antistatic film such as a metal film or a doped semiconductor film in advance when ion implantation is performed. This method requires a complicated process for patterning the conductive antistatic film, and is costly. Further, in the case where a metal is used as an ion implantation mask and the case where a metal is used as a conductive film, there is a possibility that the performance and yield of a semiconductor device are lowered due to the incorporation of metal impurities into a semiconductor substrate.
Patent document 5 describes a method of using a thin metal film of titanium, molybdenum, or the like as an ion implantation mask. In this means, since the metal thin film has excellent heat resistance and conductivity, ion implantation can be performed at high temperature without causing a problem of electrification. On the other hand, patterning of a thin metal film of titanium, molybdenum, or the like requires a complicated process and is costly. Further, in the case where a metal is used as an ion implantation mask, there is a possibility that the performance and yield of the semiconductor device are lowered due to the incorporation of metal impurities into the semiconductor substrate.
Patent document 6 describes a means for obtaining a pattern of a calcined polysiloxane on a substrate by patterning a photosensitive resin composition containing polysiloxane on the substrate and then thermally calcining the patterned composition. This method can form an ion implantation mask pattern having heat resistance up to 1000 ℃ on a substrate, but the calcined polysiloxane has no conductivity, and thus the problem of charging at the time of ion implantation cannot be solved.
In view of the background described above, the present invention provides a photosensitive resin composition which has high-temperature heat resistance and conductivity, does not cause a risk of generation of metal impurities in a semiconductor substrate, can be subjected to pattern formation, and can be applied to a high-temperature ion implantation process at low cost.
Means for solving the problems
The present inventors have conceived the following invention in view of the above problems.
A photosensitive resin composition comprising a photosensitive resin and particles of a conductive material and/or a semiconductor material.
The composition according to the above < 1 >, wherein the aforementioned particles are particles of a metal, a semimetal, or a combination thereof.
The composition according to the above < 2 >, wherein the particles are silicon particles.
The composition according to the above < 3 >, wherein the silicon particles contain at least one element among group 13 and group 15 elements as a dopant.
The composition according to the above < 4 >, wherein the silicon particles contain boron or phosphorus as a dopant.
< 6 > the composition according to the above < 4 > or < 5 >, wherein the concentration of the dopant in the silicon particles is 1018Atom/cm3The above.
The composition according to any one of the above < 3 > - < 6 >, wherein the content of metallic impurities is 100ppb or less for each metallic element.
The composition according to any one of the above < 1 > -7 >, wherein the average particle size of the particles is 1 to 500 nm.
The composition according to the above < 8 >, wherein the average particle size of the particles is 1 to 100 nm.
< 10 > the composition according to any one of the above < 1 > -9 >, wherein when a film of the photosensitive resin composition is fired at 800 ℃ for 1 hour under the atmosphere to obtain a mask layer having a film thickness of 0.5 μm, the mask layer has a sheet resistance of 1012Omega/□ or less.
The composition according to any one of the above < 1 > - < 10 >, which further contains a silicone compound.
A method for manufacturing a semiconductor device of < 12 >, comprising:
a step of forming a pattern of a film of the photosensitive resin composition described in any one of the above < 1 > to < 11 > on a semiconductor layer or a base material;
a step of forming an ion implantation mask by baking a pattern of the film of the photosensitive resin composition;
implanting ions into the semiconductor layer or the base material through the pattern openings of the ion implantation mask; and
and removing the ion implantation mask.
The method according to the above < 12 >, wherein the step of forming a pattern of the film of the photosensitive resin composition on the semiconductor layer or the substrate comprises: forming a film of the photosensitive resin composition described in any one of the above-mentioned < 1 > - < 11 > on a semiconductor substrate, and pattern-forming, exposing and developing the film of the photosensitive resin composition.
The method according to the above < 12 > or < 13 >, wherein the semiconductor layer or the substrate is an SiC layer or substrate.
The method according to any one of the above < 12 > - < 14 >, wherein the temperature of the semiconductor layer or the substrate in the ion implantation step is 200 ℃ or more.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the photosensitive resin composition of the present invention, in the high-temperature ion implantation process, the process can be more easily performed than the conventional process, and a low-cost production process can be provided. Further, according to the photosensitive resin composition of the present invention, a manufacturing process capable of omitting an antistatic device necessary for antistatic in a conventional ion implantation process or an antistatic process on a semiconductor device can be provided. Therefore, according to the manufacturing method of the present invention, it is possible to provide a manufacturing process of a power semiconductor, which is higher in productivity and yield and lower in cost than the conventional method.
Drawings
Fig. 1 is a schematic view of a process of ion implantation in the present invention.
Fig. 2 is a schematic diagram of a process of ion implantation in the prior art.
Fig. 3 shows a graph of the Al concentration distribution in the depth direction obtained by SIMS measurement.
Detailed Description
Photosensitive body resin composition
The photosensitive resin composition of the present invention contains a photosensitive resin and particles of a conductive material and/or a semiconductor material.
The photosensitive resin used in the photosensitive resin composition of the present invention can be selected to have negative or positive photosensitivity, and particularly, a photosensitive resin used for forming an ion implantation mask can be used. The photosensitive resin composition of the present invention can be used for obtaining a mask used in an ion implantation step.
Particles of conductive and/or semiconductive materials
The conductive material and/or semiconductor material constituting the particles used in the present invention may be selected such that: when an ion implantation mask is formed using the photosensitive resin composition of the present invention and ion implantation is performed, the mask has sufficient conductivity to suppress charging (charge-up) occurring in the semiconductor layer or the substrate and the ion implantation mask.
As the particles used in the present invention, a single kind of particles may be used, or 2 or more kinds of particles may be used in combination.
Specifically, the conductive material and/or the semiconductor material may be selected to have a thickness of, for example, 1 × 10121 × 10 at a value of not more than Ω m91 × 10 at a value of not more than Ω m61 × 10 at a value of not more than Ω m3Omega m or less, 1X 10-3Omega m or less, or 1X 10-6A material having a resistivity of not more than Ω m.
Of these, the conductive material and/or the semiconductor material may be selected to have a thickness of preferably 1 × 10 from the viewpoint of preventing charging even in an ion implantation step with high throughput at a high beam density of 100mA order3Ω m or less, more preferably 1 Ω m or less, and still more preferably 1 × 10-3Omega m or less, particularly preferably 1X 10-6A material having a resistivity of not more than Ω m.
Further, the conductive material and/or the semiconductor material may be selected so that when a film of the photosensitive resin composition is fired at 800 ℃ for 1 hour under the atmosphere to obtain a mask layer having a film thickness of 0.5 μm, the mask layer has a sheet resistance of 101210 below omega/□11Omega/□ or less, or 1010Omega/□ or less.
The particles used in the present invention are preferably particles of a material having a melting point exceeding the temperature of the semiconductor layer or the substrate in the ion implantation step, from the viewpoint of stabilizing the pattern shape in the ion implantation step.
Thus, for example, particles of a material having a melting point of, for example, 400 ℃ or higher, 600 ℃ or higher, 800 ℃ or higher, 1000 ℃ or higher, 1200 ℃ or higher, or 1500 ℃ or higher can be used as the particles used in the present invention.
The average primary particle diameter of the particles used in the present invention may be 500nm or less, 200nm or less, 100nm or less, 50nm or less, 20nm or less, or 5nm or less. The average primary particle diameter of the particles used in the present invention may be 1nm or more, 3nm or more, 5nm or more, 10nm or more, or 20nm or more.
The average primary particle size of the particles used in the present invention is preferably 200nm or less, 100nm or less, 50nm or less, 20nm or less, or 5nm or less in order to suppress light scattering during pattern formation exposure and reduce pattern penetration.
In the present invention, the average primary particle diameter of the particles can be determined as the number-average primary particle diameter by directly measuring the projected area circle equivalent diameter based on an image obtained by observation with a Scanning Electron Microscope (SEM), a Transmission Electron Microscope (TEM), or the like, and analyzing a group of particles whose aggregate number is 100 or more.
As the particles used in the present invention, particles of a metal, a semimetal, or a combination thereof can be used. Here, examples of the semimetal include silicon and germanium.
In the step of heating the semiconductor layer or the substrate to a high temperature and performing ion implantation, in order to prevent contamination of the semiconductor layer or the substrate with metal impurities, it is preferable to use particles of a semiconductor material, particularly particles of the same semiconductor material as the semiconductor layer or the substrate.
Therefore, for example, the particles used in the present invention are particles of semiconductor materials such as silicon (Si), germanium (Ge), diamond (C), silicon carbide (SiC), silicon germanium (SiGe), gallium nitride (GaN), indium phosphide (InP), gallium arsenide (GaAs), cadmium sulfide (CdS), zinc selenide (ZnSe), zinc oxide (ZnO), and the like.
The particles of semiconductor material, in particular silicon particles, can be doped beforehand with an impurity dopant and thus have a preferred conductivity.
The particles of the semiconductor material, particularly the silicon particles, at this time may contain at least one element among group 13 and group 15 elements as a dopant. That is, the dopant may be P-type or n-type, and may contain, for example, a dopant selected from boron (B), aluminum (Al), gallium (Ga), indium (In), titanium (Ti), iron (Fe), phosphorus (P), arsenic (As), antimony (Sb), or a combination thereof, or a dopant of, for example, boron or phosphorus.
In particular, when the silicon particles contain boron as a dopant, boron provides a conductivity preferable for the silicon particles, and on the other hand, boron is preferable in that it is difficult to move from the silicon particles to the semiconductor substrate in the ion implantation step.
The concentration of the dopant in the semiconductor particles, in particular silicon particles, may be 1018Atom/cm3Above, 1019Atom/cm3Above, or 1020Atom/cm3The above.
In the step of heating the semiconductor layer or the substrate to a high temperature and performing ion implantation, in order to prevent contamination of the semiconductor layer or the substrate with metal impurities, semiconductor particles in which the concentration of the metal impurities contained in the semiconductor particles is 100ppb or less, 50ppb or less, 20ppb or 10ppb or less for each metal element may be used. Here, when the semiconductor is a compound semiconductor including a metal as a constituent element, the "metal impurity" refers to a metal other than the metal constituting the semiconductor.
The particles used in the present invention may be used at any concentration within a range in which a mask for ion implantation can be formed. For example, the particles used in the present invention are preferably used in a proportion of 1 wt% to 90 wt% with respect to the photosensitive resin composition. By setting the concentration of the particles to 90% by weight or less, the pattern formation of the photosensitive resin composition film can be performed without a significant decrease in photosensitivity of the photosensitive resin composition. Further, by setting the concentration of the conductive particles to 1 wt% or more, the photosensitive resin composition film is fired to exert performance as an ion implantation mask layer, and therefore, an ion implantation mask having a sufficient film thickness can be formed.
The particles used in the present invention are preferably particles obtained by a laser pyrolysis method. When silicon particles obtained by the laser pyrolysis method are used, for example, particles described in JP 2010-514585A can be used.
The silicon particles obtained by the laser pyrolysis method are characterized by having high circularity of primary particles. Specifically, the circularity may be 0.80 or more, 0.90 or more, 0.93 or more, 0.95 or more, 0.97 or more, 0.98 or more, or 0.99 or more. The circularity can be calculated from (4 π S)/l by measuring the projected area (S) of the particle and the perimeter (l) of the particle by image processing software or the like from an image taken by observation with a Scanning Electron Microscope (SEM), a Transmission Electron Microscope (TEM), or the like2And thus found. In this case, the circularity can be determined as an average value of 100 or more particle groups.
Further, as the characteristics of the silicon particles obtained by the laser pyrolysis method, there is a case where the inside of the particles is in a crystal state and the surface portion of the particles is in an amorphous state. Thus, specific physical properties can be imparted to various articles using the particles. In the present invention, silicon particles in which the inside of the particles is in a crystalline state and the surface of the particles is in an amorphous state can also be suitably used.
Solvent (solvent)
The photosensitive resin composition of the present invention may further contain a solvent. The type of the solvent is not particularly limited, and a solvent capable of dissolving the components contained in the photosensitive resin composition and uniformly dispersing the particles used in the present invention is preferably selected.
The boiling point of the solvent contained in the photosensitive resin composition of the present invention under atmospheric pressure is preferably 110 ℃ to 250 ℃. By selecting a solvent having a boiling point of 110 ℃ or higher, the solvent is evaporated at an appropriate rate during film formation of the photosensitive resin composition film, and a uniform film can be obtained. Further, by selecting a solvent having a boiling point of 250 ℃ or lower, the solvent remaining in the film of the photosensitive resin composition can be reduced after the film of the photosensitive resin composition is formed, and therefore, cracks and a decrease in surface flatness due to film shrinkage during firing can be suppressed.
Adhesive
The photosensitive resin composition of the present invention may contain a binder in order to bind particles to each other in the step of calcining the photosensitive resin composition to form a stable ion implantation mask. Examples of the binder used in the photosensitive resin composition of the present invention include a polysiloxane compound and spin on glass (spin on glass).
Method for manufacturing semiconductor device
The method of the present invention for manufacturing a semiconductor device includes the steps of:
a step of forming a pattern of a film of the photosensitive resin composition of the present invention on a semiconductor layer or a substrate;
a step of forming an ion implantation mask by baking a pattern of a film of a photosensitive resin composition;
implanting ions into the semiconductor layer or the base material through the pattern openings of the ion implantation mask; and
and removing the mask for ion implantation.
Here, the step of forming a pattern of a film of the photosensitive resin composition on the semiconductor layer or the substrate may include: a film of the photosensitive resin composition of the present invention is formed on a semiconductor substrate, and the film of the photosensitive resin composition is subjected to pattern formation exposure and development.
An example of the method of the present invention for manufacturing a semiconductor device is described below with reference to fig. 1.
First, as shown in fig. 1(a), a SiC substrate (2) having a SiC epitaxial growth film (1) is provided, and as shown in fig. 1(b), a film (11) of a photosensitive resin composition is formed on the SiC substrate by an arbitrary method.
Thereafter, the photosensitive resin composition film is subjected to pattern formation exposure by light or the like having sensitivity to the photosensitive resin composition, and the SiC substrate having the photosensitive resin composition film is immersed in a developer or the like, whereby the soluble portion in the photosensitive resin composition film obtained through the pattern formation exposure step is removed. Thus, as shown in fig. 1(c), a film of the photosensitive resin composition having mask pattern openings (12) is patterned on the SiC substrate (2).
Thereafter, as shown in fig. 1(d), the SiC substrate on which the film of the photosensitive resin composition is formed is fired at a temperature at which the organic component contained in the photosensitive resin composition is decomposed, whereby an ion implantation mask (13) can be obtained.
Thereafter, as shown in fig. 1(e), the surface of the SiC substrate (2) is ion-implanted with a beam (7) of dopant ions through a mask pattern opening (12) of an ion implantation mask (13) using an ion implantation apparatus, thereby forming an ion-implanted region (6). At this time, the semiconductor layer or the substrate to be ion-implanted is heated to a temperature of 200 ℃ or higher, whereby the ion implantation step can be performed.
Thereafter, as shown in fig. 1(f), the ion implantation mask (13) can be removed by means of immersion in a chemical solution or the like capable of dissolving the mask.
Semiconductor layer or substrate
As the semiconductor layer or the substrate, any semiconductor layer or substrate intended to diffuse a dopant may be used.
Therefore, examples of the semiconductor layer or the substrate include, but are not limited to, silicon (Si), germanium (Ge), diamond (C), silicon carbide (SiC), silicon germanium (SiGe), gallium nitride (GaN), indium phosphide (InP), gallium arsenide (GaAs), cadmium sulfide (CdS), zinc selenide (ZnSe), zinc oxide (ZnO), and particularly silicon carbide (SiC).
The semiconductor layer or the substrate may be composed of a single layer, or may be a laminate composed of 2 or more layers including 1 or more semiconductor layers. Such a stacked body may be a semiconductor stacked body having an epitaxial growth film such as an SiC epitaxial growth film grown for the purpose of obtaining desired semiconductor device characteristics on a semiconductor single crystal substrate such as an SiC single crystal substrate.
The semiconductor layer or substrate may be doped with 10 of an impurity dopant16Atom/cm3The semiconductor layer or the substrate may be previously doped with an impurity dopant of more than 10 deg.C16Atom/cm3Is doped.
A metal film or a metal wiring pattern may be formed in advance on the semiconductor layer or the substrate.
(step of Forming film Pattern of photosensitive resin composition)
In the method of the present invention for manufacturing a semiconductor device, a film of the photosensitive resin composition of the present invention is patterned on a semiconductor layer or a substrate.
This step may include: a film of the photosensitive resin composition of the present invention is formed on a semiconductor substrate, and the film of the photosensitive resin composition is subjected to pattern formation exposure and development.
The film of the photosensitive resin composition of the present invention can be formed on the semiconductor substrate by any means capable of forming a film of the photosensitive resin composition on the semiconductor layer or the substrate. Examples of such means include spin coating, slit coating, spray coating, and lamination in which a photosensitive resin composition film prepared in advance on another substrate is transferred onto a semiconductor substrate, but any means not limited thereto may be selected.
When the photosensitive resin composition contains a solvent, the photosensitive resin composition may be baked to remove the solvent after the film is formed. As a means for heating and removing the solvent, any heating method such as an oven, a hot plate, or infrared rays can be used.
(film thickness of photosensitive resin composition film)
The thickness of the photosensitive resin composition film can be selected to be any thickness. The film thickness varies depending on the composition of the photosensitive resin composition, coating conditions, coating method, and the like, and may be applied so that the film thickness of the photosensitive resin composition film is 0.1 μm to 100 μm, for example.
After the film of the photosensitive resin composition is patterned, it is preferably baked to have a sufficient film thickness as a mask layer for ion implantation, from the viewpoint of utilization as a mask layer for ion implantation. Therefore, the film thickness of the film of the photosensitive resin composition can be selected so that the resulting mask for ion implantation has a film thickness having sufficient ion blocking ability, taking into consideration factors such as the temperature of the semiconductor substrate, the acceleration voltage of ions, and the length of penetration of dopant ions into the ion implantation during the ion implantation.
(Pattern formation Exposure)
The photosensitive resin composition film can be subjected to pattern formation exposure by any means corresponding to the resist.
The exposure refers to irradiation of active chemical rays which are photosensitive to the photosensitive resin composition, and examples thereof include irradiation with visible rays, ultraviolet rays, electron rays, and X-rays. From the viewpoint of being a light source generally used, for example, an ultra-high pressure mercury lamp light source capable of irradiating visible light rays or ultraviolet rays is preferably used, and j-line (wavelength 313nm), i-line (wavelength 365nm), h-line (wavelength 405nm), or g-line (wavelength 436nm) is preferable.
Next, the following development prebaking may be performed as necessary. By performing the development prebaking, effects such as improvement of resolution at the time of development and increase of allowable range of development conditions can be expected. The baking temperature at this time is preferably 50 to 180 ℃, and more preferably 60 to 150 ℃. The baking time is preferably 10 seconds to several hours. If the amount is within the above range, the reaction proceeds well, and the development time can be shortened.
(development)
Subsequently, the pattern of the photosensitive resin composition can be obtained by development after pattern formation and exposure. For example, if a film of the photosensitive resin composition after exposure is pattern-formed by immersing the photosensitive resin composition in a developer, the pattern formation of the film of the photosensitive resin composition can be performed by removing the unexposed portions when the photosensitive resin composition has negative photosensitivity and removing the exposed portions when the photosensitive resin composition has positive photosensitivity.
The developer may be any developer selected according to the composition of the photosensitive resin composition. A developer showing alkaline liquid properties can be preferably used, and for example, tetramethylammonium hydroxide, potassium hydroxide, and sodium hydroxide can be preferably used.
From the environmental point of view, development with an aqueous alkali solution is desired as compared with an organic alkali developing solution.
Further, in order to improve the dissolution of the pattern forming part and the dispersibility of the conductive particles, the developing solution may contain a solvent. As examples of the solvent in this case, isopropyl alcohol, acetone, propylene glycol 1-monomethyl ether 2-acetate, and the like can be preferably used.
The developer may contain a surfactant to improve dissolution of the pattern forming portion and dispersibility of the conductive particles.
The development treatment can be performed by a method such as directly applying the developer to the exposed film, emitting the developer in a mist form, immersing the exposed film in the developer, and applying ultrasound while immersing the exposed film in the developer.
After the development treatment, the relief pattern formed by the development is preferably washed with a rinse solution. When an aqueous alkali solution is used as the rinse solution for the developer, water can be preferably used. In addition, alcohols such as ethanol and isopropyl alcohol, esters such as propylene glycol monomethyl ether acetate, carbonic acid gas, hydrochloric acid, acetic acid, and the like may be added to water to perform rinsing treatment.
When rinsing with an organic solvent, methanol, ethanol, isopropanol, ethyl lactate, ethyl pyruvate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 2-heptanone, ethyl acetate, and the like, which have good compatibility with the developer, are preferably used.
When the photosensitive resin composition has positive photosensitivity, it may be subjected to fading exposure without a mask, if necessary. By performing the fading exposure, effects such as improvement of the resolution after firing, control of the pattern shape after firing, and improvement of the transparency after firing can be expected. As the active chemical rays used for the exposure for color fading, there are ultraviolet rays, visible light rays, electron rays, X-rays, etc., and in the present invention, j-line (wavelength of 313nm), i-line (wavelength of 365nm), h-line (wavelength of 405nm), or g-line (wavelength of 436nm) of a mercury lamp is preferably used.
Subsequently, intermediate baking may be performed as necessary. By performing the intermediate baking, effects such as improvement in resolution after the baking and control of a pattern shape after the baking can be expected. The baking temperature at this time is preferably 60 to 250 ℃, and more preferably 70 to 220 ℃. The baking time is preferably 10 seconds to several hours.
Formation step of mask for ion implantation
In the method of the present invention, the pattern of the film of the photosensitive resin composition is then fired to form an ion implantation mask.
It can be carried out by heating the developed film at a temperature of 200 to 1000 ℃. The heat treatment may be performed in an air atmosphere or an inert gas atmosphere such as nitrogen. The heat treatment is preferably performed for 5 minutes to 5 hours by raising the temperature stepwise or continuously. For example, a method of performing heat treatment at 130 ℃, 200 ℃ and 350 ℃ for 30 minutes, or performing linear temperature rise from room temperature to 400 ℃ over 2 hours may be mentioned.
Ion implantation step
In the method of the present invention, ions are then implanted into the semiconductor layer or the substrate through the pattern openings of the ion implantation mask.
The ion implantation mask is preferably used in a process for manufacturing a semiconductor device including ion implantation into a SiC layer or a substrate having an ion implantation temperature of 200 to 1000 ℃. The ion implantation temperature is preferably 200 to 1000 ℃, more preferably 200 to 800 ℃, further preferably 250 to 700 ℃, and particularly preferably 300 to 500 ℃.
When the semiconductor layer or the substrate is an SiC layer or a substrate, if the ion implantation temperature is lower than 200 ℃, the implanted layer forms a continuous amorphous layer, and even if high-temperature annealing is performed, favorable recrystallization may not be performed, and a low-resistance layer may not be formed. Further, at this time, if the ion implantation temperature is higher than 1000 ℃, thermal oxidation of SiC, step coalescence are caused, and therefore it becomes necessary to remove these portions after ion implantation.
The resolution when the photosensitive resin composition of the present invention is applied to an ion implantation mask application is preferably 7 μm or less, more preferably 5 μm or less, and still more preferably 3 μm or less.
Ion implantation mask removal step
The ion implantation mask is removed after the ion implantation step. Examples of the removal method include a wet process using hydrofluoric acid, buffered hydrofluoric acid, hydrofluoric acid-nitric acid, TMAH, or the like, a dry process such as plasma treatment, and the like, but are not limited thereto. From the viewpoint of low cost, a wet process is preferable.
Examples
Examples 1 to 2 and comparative examples 1 to 3
In examples 1 to 2 and comparative examples 1 to 3 below, a photosensitive resin composition was prepared, a coating film was formed on a SiC substrate, and then pattern formation of an ion implantation mask obtained therefrom was performed by pattern formation exposure with ultraviolet light, development, and calcination. In addition, in the examples and comparative examples, the evaluation was made as to whether or not patterning can be performed, whether or not a pattern remains after thermal firing, and whether or not there is a problem due to charging at the time of ion implantation.
EXAMPLE 1
(production of boron (B) -doped silicon particles)
The silicon nanoparticles are produced by a Laser Pyrolysis (LP) method using a carbon dioxide Laser using monosilane gas as a raw material. At this time, diborane (B) is introduced together with monosilane gas2H6) And (5) gas is carried out, so as to obtain the boron-doped silicon particles. The particle size of the particles was 20 nm.
The doping concentration of the obtained boron-doped silicon particles is 1 multiplied by 1021Atom/cm3. Further, when the metal impurity content of the obtained boron-doped silicon particles was measured by an inductively coupled plasma mass spectrometer (ICP-MS), the content of Fe was 15ppb, the content of Cu was 18ppb, the content of Ni was 10ppb, the content of Cr was 21ppb, the content of Co was 13ppb, the content of Na was 20ppb, and the content of Ca was 10 ppb.
(preparation of solution containing boron-doped silicon particles)
A solution of boron-containing doped silicon particles was prepared by mixing 95 wt% of isopropyl alcohol and 5 wt% of the silicon nanoparticles produced by the above-described procedure.
(preparation of photosensitive resin composition containing silicon nanoparticles and negative photosensitive resin)
A negative photoresist (CTP-100T, メルクパフォーマスンスマテリアルズマニュファクチャリング, manufactured by kokai) and the solution containing boron-doped silicon particles were mixed to prepare a photosensitive resin composition containing silicon nanoparticles and a negative photosensitive resin. At this time, the photosensitive resin composition was prepared such that the boron-doped silicon nanoparticles accounted for 20 wt% of the solid content of the photosensitive resin composition after mixing.
(formation of photosensitive resin composition film)
The photosensitive resin composition containing the silicon nanoparticles and the negative photosensitive resin was spin-coated on a SiC substrate at a spin speed at which the film thickness reached about 2 μm, and dried on a hot plate at 100 ℃ for 90 seconds, thereby obtaining a photosensitive resin composition film.
(Pattern formation)
The photosensitive resin composition film is subjected to pattern formation exposure by irradiating ultraviolet light through a photomask pattern using a pattern formation exposure machine. As the photomask, pattern formation exposure was performed using a photomask having lines and spaces of 10 μm. The photosensitive resin composition film after pattern formation and exposure was heated on a hot plate at 100 ℃ for 90 seconds, and then immersed in a developer (AZ-300MIF, manufactured by メルクパフォーマスンスマテリアルズマニュファクチャリング, Co., Ltd.) for 60 seconds to develop a pattern. After the development, the substrate with the photosensitive resin composition film was washed with running pure water, and then the substrate was dried to form a pattern of the photosensitive resin composition film on the SiC substrate.
(observation Using an optical microscope)
The formed photosensitive resin composition film was observed with an optical microscope for the pattern, and it was confirmed whether a 10 μm line and space pattern could be formed.
(calcination)
The pattern of the photosensitive resin composition film was fired in an oven at 800 ℃ for 1 hour under the air, thereby forming an ion implantation mask on the SiC substrate. The thickness of the mask layer for ion implantation after the calcination was 0.5 μm.
(observation Using an optical microscope)
The presence or absence of pattern formation in the ion implantation mask after firing was confirmed using an optical microscope.
(ion implantation)
Ion implantation was performed on the SiC substrate through the mask pattern openings of the ion implantation mask after the firing under the following conditions:
ion species: al, Al,
Energy amount: 40keV,
Injection temperature: at 400 deg.C,
Dosage: 1X 1014Ion/cm2
After the Al ion implantation, the substrate is immersed in a buffered mixed solution of hydrofluoric acid and concentrated sulfuric acid, thereby removing the ion implantation mask. Thereafter, the depth dependence from the surface of the SiC substrate of the Al concentration was measured using a Secondary Ion Mass Spectrometry (SIMS) apparatus.
SIMS measurement was performed on the surface of the SiC substrate in the opening region of the ion implantation mask at the time of Al ion implantation and the region covered with the ion implantation mask layer at the time of Al ion implantation, among the SiC substrates subjected to ion implantation. Fig. 3 shows the Al concentration distribution in the depth direction obtained by SIMS measurement.
As shown in FIG. 3, in the Al concentration distribution (21) of the opening region of the ion implantation mask at the time of Al ion implantation, a concentration of 1.5X 10 in the vicinity of a depth of 50nm was observed19Atom/cm3The profile of the peak of (a). On the other hand, in the Al concentration distribution (22) of the region covered with the mask layer for ion implantation at the time of Al ion implantation, the Al concentration is 5.5X 10 even at the surface where the highest Al concentration is detected17Atom/cm3And is about 1/30 of the peak concentration in the Al concentration distribution (21) in the opening region of the ion implantation mask at the time of Al ion implantation. Further, 10 detected in a range of about 100nm from the surface14~1017Personal sourceSeed/cm3Since the Al ions in (2) are determined to be caused by the influence of the surface adsorbate in the SIMS measurement, it can be determined that no Al ions implanted into SiC are detected in the region covered with the ion implantation mask layer at the time of ion implantation. Therefore, it can be determined that Al ions are not implanted into the SiC substrate in the region covered with the ion implantation mask layer during Al ion implantation.
From the above results of the SIMS measurement, it can be understood that the mask layer for ion implantation in the present embodiment has an effect of shielding implanted ions during ion implantation, since Al ions are implanted into the SiC substrate surface in the opening region of the ion implantation mask during Al ion implantation, while Al ions are not implanted into the SiC substrate surface in the region covered with the ion implantation mask during Al ion implantation.
EXAMPLE 2
A mask layer was formed on a SiC substrate in the same manner as in example 1 except that a negative resist (CTP-100T, manufactured by メルクパフォーマスンスマテリアルズマニュファクチャリング contract) and a solution of the boron-doped silicon particles were mixed as the photosensitive resin composition, and a solution of the boron-doped silicon particles and a spun silica (12000-T, manufactured by tokyo seiki industries, ltd.) were mixed instead of the negative resist (CTP-100T, manufactured by メルクパフォーマスンスマテリアルズマニュファクチャリング contract). At this time, the photosensitive resin composition was prepared such that the boron-doped silicon nanoparticles accounted for 10 wt% and the solid component contained in the spun silica solution accounted for 10 wt% of the solid component amount of the photosensitive resin composition after mixing.
Comparative example 1
As the photosensitive resin composition, a negative resist (CTP-100T, manufactured by メルクパフォーマスンスマテリアルズマニュファクチャリング), SiO, instead of the negative resist (CTP-100T, manufactured by メルクパフォーマスンスマテリアルズマニュファクチャリング Corp.) and the boron-doped silicon particle-containing solution, were mixed2Nano meterA mask layer was formed on the SiC substrate in the same manner as in example 1 except that the particle dispersion solution SIRPMA30WT% -E9 (manufactured by CIK ナノテック co., ltd.). At this time, the photosensitive resin composition is prepared so that SiO is contained in the solid content of the mixed photosensitive resin composition2The solid component contained in the nanoparticle dispersion solution SIRPMA30WT% -E9 accounted for 20% by weight.
Comparative example 2
A mask layer was formed on a SiC substrate in the same manner as in example 1 except that a negative resist (CTP-100T, manufactured by メルクパフォーマスンスマテリアルズマニュファクチャリング), a solution containing boron-doped silicon particles, and a spun-on silicon oxide (12000-T, manufactured by tokyo chemical corporation) were mixed as the photosensitive resin composition instead of the negative resist (CTP-100T, manufactured by メルクパフォーマスンスマテリアルズマニュファクチャリング), and the solution. At this time, the photosensitive resin composition was prepared such that the solid content contained in the spun silica accounted for 20% by weight among the solid content of the photosensitive resin composition after mixing.
Comparative example 3
A step of forming a mask layer on a SiC substrate was carried out in the same manner as in example 1 except that a negative photoresist (CTP-100T, manufactured by メルクパフォーマスンスマテリアルズマニュファクチャリング contract) was used as the photosensitive resin composition instead of the solution obtained by mixing the negative photoresist (CTP-100T, manufactured by メルクパフォーマスンスマテリアルズマニュファクチャリング contract) and the solution containing boron-doped silicon particles.
The experimental conditions and results for examples 1-2 and comparative examples 1-3 are summarized in Table 1 below.
[ Table 1]
Figure 969891DEST_PATH_IMAGE002
Evaluation results
From the results of examples 1 to 2 and comparative examples 1 to 3, it is understood that when silicon (Si) particles are used as an additive, a pattern of a residue having conductivity can be formed on a substrate by thermal calcination after patterning of a photosensitive resin composition, and Silica (SiO) having no conductivity is added as an additive2) Particles and spun silica cannot form a pattern of conductive residue on the substrate.
Further, it can be understood from the results of examples 1 to 2 that by mixing spun silica as a binder in addition to silicon nanoparticles having conductivity as an additive, a pattern having a conductive residue can be formed on a substrate by thermal calcination after patterning of the photosensitive resin composition.
EXAMPLE 3 and COMPARATIVE EXAMPLE 4
In the following example 3 and comparative example 4, a photosensitive resin composition was prepared, a coating film was formed on a substrate having a thermal silicon oxide film of 1000nm, and then pattern formation of a mask layer was performed by pattern formation exposure with ultraviolet light, development, and calcination. In addition, in these examples and comparative examples, the sheet resistance of the mask layer was measured.
EXAMPLE 3
Patterning of the mask layer was performed in the same manner as in example 1, except that a silicon wafer having a thermal silicon oxide film of 1000nm was used as the substrate instead of the SiC substrate, and the entire surface of the substrate was exposed to ultraviolet light during the patterning exposure. After the mask layer was patterned, an aluminum electrode for the purpose of measuring the resistivity of the mask layer pattern was formed on the mask layer pattern by a vacuum deposition method through a shadow mask.
As a pattern of an aluminum electrode for the purpose of measuring resistivity, an electrode pattern was used in which a set of rectangular electrodes having a size of 1000 μm × 200 μm were arranged such that sides of 1000 μm were opposed to each other at intervals of 200 μm.
Then, the sheet resistance of the mask layer was determined by measuring the potential drop between the aluminum electrodes when a constant current of 1 μ A was applied between the deposited aluminum electrodes, and was 90G Ω/□.
Comparative example 4
An ion implantation mask having a pattern was formed on a silicon substrate in the same manner as in example 3 except that spun silicon oxide (12000-T, manufactured by tokyo chemical industries, ltd.) was used instead of the solution containing boron-doped silicon particles, and then the sheet resistance of the ion implantation mask was measured. Accordingly, the current not lower than the measurement limit of the device could not be measured, and the sheet resistance of the mask layer was estimated to be 2.0 × 108G omega/□ or more.
Description of the reference numerals
1 SiC epitaxial growth film
2 SiC substrate
3 SiO2Film
4 photo-sensitive resist
6 ion implantation region
7 beams of dopant ions
11 photosensitive resin composition film
12 mask pattern opening
13 mask layer pattern
21 Al concentration distribution in opening region of mask layer for ion implantation in ion implantation of Al
22 Al concentration distribution of region covered by mask layer for ion implantation in Al ion implantation

Claims (12)

1. A photosensitive resin composition contains a photosensitive resin and silicon particles containing at least one element selected from group 13 and group 15 elements as a dopant.
2. The composition of claim 1, wherein the silicon particles contain boron or phosphorus as a dopant.
3. The composition of claim 1 or 2, wherein the concentration of the dopant in the silicon particles is 1018Atom/cm3The above。
4. The composition according to claim 1 or 2, wherein the content of metal impurities is 100ppb or less for each metal element.
5. The composition according to claim 1 or 2, wherein the particles have an average particle diameter of 1 to 500 nm.
6. The composition according to claim 5, wherein the particles have an average particle diameter of 1 to 100 nm.
7. The composition according to claim 1 or 2, wherein when the film of the photosensitive resin composition is fired at 800 ℃ for 1 hour under the air atmosphere to obtain a mask layer having a film thickness of 0.5 μm, the mask layer has a sheet resistance of 1012Omega/□ or less.
8. The composition of claim 1 or 2, further comprising a silicone compound.
9. A method of manufacturing a semiconductor device, comprising:
a step of forming a pattern of a film of the photosensitive resin composition according to any one of claims 1 to 8 on a semiconductor layer or a substrate;
a step of forming an ion implantation mask by baking a pattern of the film of the photosensitive resin composition;
implanting ions into the semiconductor layer or the base material through a pattern opening of the ion implantation mask; and
and removing the mask for ion implantation.
10. The method according to claim 9, wherein the step of forming a pattern of the film of the photosensitive resin composition on the semiconductor layer or the substrate comprises: forming a film of the photosensitive resin composition according to any one of claims 1 to 8 on a semiconductor layer or a substrate, and subjecting the film of the photosensitive resin composition to pattern formation exposure and development.
11. The method of claim 9 or 10, wherein the semiconductor layer or substrate is a SiC layer or substrate.
12. The method according to claim 11, wherein the temperature of the SiC layer or substrate in the ion implantation step is 200 ℃ or higher.
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WO2015146749A1 (en) * 2014-03-26 2015-10-01 東レ株式会社 Method for manufacturing semiconductor device and semiconductor device

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