JP2013105991A - Semiconductor laminate, semiconductor device and manufacturing methods of those - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a semiconductor laminate including a semiconductor silicon film with high continuity without requiring an expensive, energy-intensive and large-scale device; and provide a semiconductor laminate having a semiconductor silicon film with high continuity.SOLUTION: A semiconductor laminate manufacturing method comprises: a step of forming a silicon particle dispersion film on a surface of a base material; a step of dehydrating the silicon particle dispersion film to form a non-sintered silicon film 120; and a step of forming a semiconductor silicon film 130a by irradiating the non-sintered silicon film with light 200. A contact angle of a molten silicon with respect to the surface 100a of the base material is 70 degrees and under. In the semiconductor laminate of the present embodiment, the semiconductor silicon film is formed from a plurality of silicon particles sintered with each other and the contact angle of the molten silicon with respect to the surface of the base material is 70 degrees and under.

Description

  The present invention relates to a base material, a semiconductor laminate having a semiconductor silicon film laminated on the base material, and a manufacturing method thereof. Moreover, this invention relates to the semiconductor device which has such a semiconductor laminated body, and its manufacturing method.

  Semiconductor silicon films, such as amorphous silicon films and polysilicon films, are used for semiconductor devices, such as thin film transistors (TFTs). When such a semiconductor silicon film is used in a semiconductor device, the semiconductor silicon film needs to have a desired pattern, for example, a circuit pattern. Therefore, in general, a semiconductor silicon film is formed on the entire surface of a substrate by a vacuum process, for example, physical vapor deposition (PVD) such as sputtering, chemical vapor deposition (CVD) such as plasma chemical vapor deposition, and thereafter Thus, unnecessary portions of the obtained semiconductor silicon film are removed by photolithography or the like to provide a semiconductor silicon film having a desired pattern.

  However, these conventional methods require a large-scale apparatus, consume a lot of energy, use efficiency of the raw material is poor (less than 5%), are difficult to handle because the raw material is a gas, In other words, it is a complicated and expensive method.

  Therefore, in recent years, a liquid phase method has been studied as a method for forming a semiconductor film for a thin film transistor or the like by a low-cost and simple process. In general, the liquid phase method uses a semiconductor material that can be applied, and thus does not require a large-scale apparatus that has been required in the past. In addition, the use efficiency of raw materials can be increased by application such as ink jetting. Simplification can be achieved.

  Regarding the production of a semiconductor film by such a liquid phase method, the use of an organic semiconductor material has been studied. However, the organic semiconductor film has insufficient performance such as carrier mobility and durability such as stability in the atmosphere as compared with the silicon semiconductor film. It is difficult to make it easier.

  In addition, regarding the production of a semiconductor film by such a liquid phase method, Patent Document 1 proposes forming a semiconductor silicon film using a dispersion containing silicon particles.

  In the liquid phase method, the use of a direct drawing technique for directly drawing a desired pattern of a semiconductor silicon film on a substrate is also being studied. Examples of the direct drawing technique include a printing method in which a raw material liquid containing a constituent material of a semiconductor silicon film is applied and printed, such as an ink jet printing method and a screen printing method.

  In such a printing method, a vacuum process is unnecessary, and pattern formation can be performed by direct drawing, so that a semiconductor device can be manufactured easily and at low cost.

Special table 2010-514585 gazette

  An object of the present invention is to provide a method for efficiently manufacturing a semiconductor silicon film at a relatively low temperature. More specifically, an object of the present invention is to provide a method of manufacturing a semiconductor stacked body having a semiconductor silicon film having high continuity without requiring an expensive and energy-consuming large-scale apparatus. .

  Moreover, the objective of this invention is providing the semiconductor laminated body which has a semiconductor silicon film with high continuity, and the semiconductor device which has such a semiconductor laminated body.

  Other objects of the present invention will become apparent from the specification and claims of the present application.

<1> A method for producing a semiconductor laminate having a substrate and a semiconductor silicon film laminated on the substrate,
(A) applying a silicon particle dispersion containing a dispersion medium and silicon particles dispersed in the dispersion medium on the surface of the substrate to form a silicon particle dispersion film;
(B) drying the silicon particle dispersion film to form an unsintered silicon film; and (c) irradiating the unsintered silicon film with light to form the unsintered silicon film in the unsintered silicon film. Sintering silicon particles, thereby forming a semiconductor silicon film;
And a contact angle of the molten silicon with respect to the surface of the base material is 70 degrees or less.
<2> The method according to <1> above, wherein the surface of the substrate is provided by a material selected from the group consisting of carbide, nitride, carbonitride, and combinations thereof.
<3> The surface of the above-mentioned <2>, wherein the surface of the base material is provided by a material selected from the group consisting of silicon carbide, silicon nitride, silicon carbonitride, graphite, and combinations thereof. Method.
<4> The above <1> to <3>, wherein the substrate has a substrate body and a surface layer, and the surface layer is made of a material having a contact angle of 70 degrees or less with molten silicon. The method as described in any one of.
<5> The method according to any one of <1> to <3>, wherein the entire base material is made of the same material as the surface of the base material.
<6> The method according to any one of <1> to <5>, wherein an average primary particle diameter of the silicon particles is 100 nm or less.
<7> The method according to any one of <1> to <6>, wherein the silicon particles are silicon particles obtained by a laser pyrolysis method.
<8> The method according to any one of <1> to <7>, wherein the light irradiation is performed in a non-oxidizing atmosphere.
<9> The method according to any one of <1> to <8>, wherein the light irradiation is performed using a laser.
<10> The method according to <9> above, wherein the wavelength of the laser is 600 nm or less.
<11> The method according to any one of <1> to <10>, wherein the light irradiation is performed using pulsed light.
<12> A method for producing a semiconductor device, comprising producing a semiconductor laminate by the method according to any one of <1> to <11> above.
<13> A semiconductor laminate obtained by the method according to any one of <1> to <11> above.
<14> A semiconductor device obtained by the method according to <13>.
<15> a substrate and a semiconductor silicon film laminated on the surface of the substrate;
The semiconductor silicon film is made of a plurality of silicon particles sintered together, and the contact angle of the molten silicon with respect to the surface of the substrate is 70 degrees or less.
Semiconductor stack.
<16> The semiconductor laminate according to <15>, wherein the semiconductor silicon film has a thickness of 50 to 500 nm.
<17> A semiconductor device having the semiconductor laminate according to <15> or <16>.
<18> A method for producing a semiconductor laminate having a substrate and a semiconductor silicon film laminated on the substrate,
(A) applying a silicon particle dispersion containing a dispersion medium and silicon particles dispersed in the dispersion medium on the surface of the substrate to form a silicon particle dispersion film;
(B) drying the silicon particle dispersion film to form an unsintered silicon film; and (c) irradiating the unsintered silicon film with light to form the unsintered silicon film in the unsintered silicon film. Sintering silicon particles, thereby forming a semiconductor silicon film;
And the surface of the substrate is provided by a material selected from the group consisting of silicon carbide, silicon nitride, silicon carbonitride, graphite, and combinations thereof.
<19> A substrate and a semiconductor silicon film laminated on the surface of the substrate,
The semiconductor silicon film is made of a plurality of silicon particles sintered together, and the surface of the substrate is made of silicon carbide, silicon nitride, silicon carbonitride, graphite, and combinations thereof. Provided by a material selected from the group,
Semiconductor stack.

  According to the method of the present invention for producing a semiconductor laminate, a semiconductor silicon film can be produced efficiently at a relatively low temperature. More specifically, according to the method of the present invention, it is possible to manufacture a semiconductor stacked body having a semiconductor silicon film having high continuity without requiring an expensive and energy-consuming large-scale apparatus.

  Moreover, the semiconductor laminated body of this invention has a semiconductor silicon film with high continuity, and can provide a preferable semiconductor characteristic by it.

It is a figure which shows the semiconductor laminated body manufactured in Example 1 and 2. FIG. 6 is a diagram showing a field effect transistor (FET) having a bottom gate / top contact structure manufactured in Example 3. FIG. 2 is a surface scanning electron microscope (SEM) photograph of a semiconductor silicon layer manufactured in (a) Example 1, (b) Example 2, and (c) Comparative Example 1. FIG. It is a figure which shows the transfer characteristic (gate voltage-drain current) of the field effect transistor (FET) manufactured in Example 3. FIG. It is a figure which shows the output characteristic (drain voltage-drain current) of the field effect transistor (FET) manufactured in Example 3. FIG. It is a figure which shows notionally the method of this invention which manufactures a semiconductor laminated body. It is a figure which shows notionally the conventional method of manufacturing a semiconductor laminated body.

<< Method for Manufacturing Semiconductor Laminate >>
The method of the present invention for producing a semiconductor laminate having a substrate and a semiconductor silicon film laminated on the substrate includes the following steps:
(A) applying a silicon particle dispersion containing a dispersion medium and silicon particles dispersed in the dispersion medium on the surface of the substrate to form a silicon particle dispersion film;
(B) drying the silicon particle dispersion film to form an unsintered silicon film; and (c) irradiating the unsintered silicon film with light to sinter the silicon particles in the unsintered silicon film. Bonding, thereby forming a semiconductor silicon film.

  In this method of the present invention, the surface of the substrate has a high affinity for the molten silicon, for example, the contact angle of the molten silicon to the surface of the substrate is 70 degrees or less, so that the silicon particles are burned with light. When bonded, a highly continuous semiconductor silicon film can be formed.

  Although not limited to the principle, it is considered that this is due to the following mechanism. That is, in the method of the present invention, as shown in FIG. 6, an unsintered silicon film (120) made of silicon particles (10) is formed on the surface of the substrate (100) (FIG. 6 (1)). Then, by irradiating the unsintered silicon film (120) with light (200), the silicon particles (10) are melted to form molten silicon (10a) (FIG. 6 (2)). At this time, if the surface of the substrate (100a) has a large affinity for the molten silicon (10a), it is considered that the molten silicon particles wet the substrate surface in situ and solidify. In this case, it is considered that the agglomeration of the molten silicon is difficult to proceed, thereby obtaining a semiconductor silicon film (130a) having high continuity (FIG. 6 (3)).

  On the other hand, as shown in FIG. 7, when the surface (100b) of the base material has a small affinity for the molten silicon (10a), the molten silicon particles are easily moved, whereby the molten silicon particles are It is thought to agglomerate and solidify. Thus, when molten silicon particles aggregate, it is thought that a semiconductor silicon film becomes discontinuous and thereby a semiconductor silicon film (130b) having low continuity is obtained (FIG. 7 (3)).

  The substrate surface having a high affinity for molten silicon may be provided by any material and is not limited as long as the object and effect of the present invention are not impaired.

  The substrate surface having a high affinity for molten silicon may be, for example, a surface having a contact angle with molten silicon of 70 degrees or less, 60 degrees or less, 50 degrees or less, or 40 degrees or less.

  The contact angle with respect to the molten silicon is an index representing the affinity of the molten silicon with respect to the base material, and is defined by the angle formed by the tangent line of the molten silicon droplet and the surface of the base material. In the context of the present invention, the contact angle with molten silicon means the contact angle measured at a steady state of 1450 ° C.

  In this regard, see, for example, the document “Wettability and reactivity of molten silicon with various substrates”, Appl. Phys. A Vol. 78, 617-622 (2004), YUAN Z. , Et. al. Then, the contact angle when silicon carbide is used as the substrate surface is 8 degrees, and the contact angle when silicon oxide is used as the substrate surface is 85 degrees.

Also, “Development and evaluation of refraction, CVD coatings as contact materials for molt silicon,” Journal of Crystal Growth, Vol. T. T. et al. Duffy et. al. And the literature “The effect of oxygen partial pressure on wetting of SiC, AlN and Si ₃ N ₄ , in Surfaces and Interfaces in Ceramic and Ceramic-Metal. J. et al. A. and A. Evans, Editors. 1981. p. 457-466. Barsouum, M .; W. et. al. In this case, the contact angle is 43 to 50 degrees when silicon nitride produced by chemical vapor deposition (CVD) is used as the substrate surface.

  The substrate surface having a high affinity for molten silicon is, for example, a material selected from the group consisting of carbide, nitride, carbonitride, and combinations thereof, particularly silicon carbide, silicon nitride, silicon carbonitride, graphite, And a material selected from the group consisting of combinations thereof. In the context of the present invention, the substrate surface with a high affinity for molten silicon may be a material other than silicon.

  An example of a material having a low affinity for molten silicon is thermally oxidized silicon oxide.

<< Manufacturing Method of Semiconductor Laminate-Step (a) >>
In step (a) of the method of the present invention, a silicon particle dispersion film containing a dispersion medium and silicon particles dispersed in the dispersion medium is applied onto the surface of the substrate to form a silicon particle dispersion film. To do.

(Base material)
The base material used by the method of this invention is not restrict | limited unless the objective and effect of this invention are impaired.

  In one aspect, the substrate has a substrate body and a surface layer, and the surface layer is made of a material that has a high affinity for molten silicon. In this case, the thickness of the surface layer is, for example, 30 nm or more, 100 nm or more, or 300 nm or more, and may be 2000 nm or less, 1000 nm or less, 700 nm or less, or 500 nm or less.

  In this case, the substrate body may consist of an inorganic material, for example doped silicon or undoped silicon.

  Further, in the method of the present invention, since the silicon particles are sintered by irradiating light, heating is limited to the surface and is extremely short. Accordingly, a base body having a relatively low heat resistance, for example, a base body having a polymer material can be used.

  Therefore, for example, as the polymer material, a polymer material containing at least one selected from the group consisting of polyimide, polyethersulfone, polycarbonate, polyethylene terephthalate, and polyethylene naphthalate can be used. Among these, a polymer material containing at least one selected from the group consisting of polycarbonate, polyethylene terephthalate and polyethylene naphthalate, particularly a polymer material containing 50% by mass or more of polycarbonate, these polymers are versatile, and It is preferable in that it is inexpensive.

  In other embodiments, the entire substrate is made of the same material as the surface of the substrate.

(Dispersion medium)
The dispersion medium of the silicon particle dispersion is not limited as long as the object and effect of the present invention are not impaired. Therefore, for example, an organic solvent that does not react with silicon particles can be used. Specifically, this dispersion medium is a non-aqueous solvent such as alcohol, alkane, alkene, alkyne, ketone, ether, ester, aromatic compound, or nitrogen-containing ring compound, particularly isopropyl alcohol (IPA), N-methyl-2. -It may be pyrrolidone (NMP) or the like. Moreover, glycol (dihydric alcohol) like ethylene glycol can also be used as alcohol. The dispersion medium is preferably a dehydrated solvent in order to suppress oxidation of silicon particles.

(Silicon particles)
The silicon particles of the silicon particle dispersion are not limited as long as the objects and effects of the present invention are not impaired. For example, silicon particles as disclosed in Patent Document 1 can be used. Specifically, examples of the silicon particles include silicon particles obtained by a laser pyrolysis method, particularly a laser pyrolysis method using a CO ₂ laser.

  The silicon particles may be silicon particles comprising a polycrystalline or single crystal core and an amorphous outer layer. In this case, a combination of semiconductor characteristics with a polycrystalline or single crystal core and ease of sintering with an amorphous outer layer can be utilized.

  The silicon particles preferably have an average primary particle diameter of 100 nm or less. Accordingly, the silicon particles may be, for example, 1 nm or more, or 5 nm or more, and 100 nm or less, 50 nm or less, or 30 nm or less. An average primary particle size of 100 nm or less is preferable in order to sinter silicon particles with light.

  The average primary particle diameter of the silicon particles is determined by directly measuring the particle diameter based on a photographed image by observation with a scanning electron microscope (SEM), a transmission electron microscope (TEM), or the like, and has an aggregate number of 100 or more. By analyzing the particle group, the number average average primary particle diameter can be obtained.

  The silicon particle dispersion used in the method of the present invention may contain a dopant such as phosphorus and boron and known additives in addition to the dispersion medium and silicon particles.

(Application)
Application of the silicon particle dispersion is not particularly limited as long as the silicon particle dispersion can be applied with a desired thickness and uniformity, and can be performed by, for example, an inkjet method, a spin coating method, or the like.

  In addition, the thickness of the green silicon film obtained when the silicon particle dispersion film is dried is 50 nm or more, 100 nm or more, or 200 nm or more, and is 2000 nm or less, 1000 nm or less, 500 nm or less, Or it can carry out so that it may be 300 nm or less. Specifically, for example, in the case of obtaining a field effect transistor (FET), coating is performed so that the thickness of the unsintered silicon film is 50 nm or more and 100 nm or more, and 500 nm or less and 300 nm or less. Can do. Moreover, when obtaining a solar cell, it is applied so that the thickness of the unsintered silicon film is 100 nm or more and 200 nm or more, and is 2000 nm or less, 1000 nm or less, 500 nm or less, or 300 nm or less. it can.

<< Manufacturing Method of Semiconductor Laminate-Step (b) >>
In step (b) of the method of the present invention, the silicon particle dispersion film is dried to form an unsintered silicon film.

(Dry)
This drying is not particularly limited as long as the dispersion medium can be substantially removed from the silicon particle dispersion film. For example, the drying is performed by placing a substrate having the silicon particle dispersion film on a hot plate. be able to.

  The drying temperature can be selected, for example, so as not to deform or deteriorate the substrate. For example, the drying temperature is 50 ° C or higher, 70 ° C or higher, 90 ° C or higher, and 200 ° C or lower, 400 ° C or lower, or 600 ° C or lower. You can choose as you like.

  Further, this drying can be performed as an integrated process with the application in the step (a). For example, the application in the step (a) can be performed by spin coating, and the application and the drying can be performed simultaneously. That is, the drying is performed only as a process integrated with the application, and may not be performed as a separate process from the application.

<< Manufacturing Method of Semiconductor Laminate-Step (c) >>
In step (c) of the method of the present invention, the unsintered silicon film is irradiated with light to sinter silicon particles in the unsintered silicon film, thereby forming a semiconductor silicon film.

(Irradiated light)
As the light irradiated here, any light can be used as long as the sintering of the silicon particles in the unsintered silicon film can be achieved. For example, laser light, particularly a wavelength of 600 nm or less, 500 nm or less, or 400 nm or less, 200 nm or more and 300 nm or more can be used. The sintering of the silicon particles can also be performed using a flash lamp such as a xenon flash lamp.

In the case of using relatively long-wavelength pulsed light (for example, YVO ₄ laser having a wavelength of 355 nm), the number of times of irradiation of the pulsed light is, for example, 1 or more, 2 or more, 5 or more, or 10 or more. And, it can be 100 times or less, 80 times or less, or 50 times or less. In this case, the irradiation energy of the pulsed light, for ^{example, 15mJ / (cm 2 · shot} ) ^{above, 50mJ / (cm 2 · shot} ) ^{above, 100mJ / (cm 2 · shot} ) above, 150 mJ / (cm ²・ Shot) or more, or 200 mJ / (cm ² · shot) or more and 2000 mJ / (cm ² · shot) or less, 1000 mJ / (cm ² · shot) or less, or 500 mJ / (cm ² · shot) or less can do. Further, in this case, the irradiation time of the pulsed light can be set to, for example, 200 nanoseconds / shot or less, 100 nanoseconds / shot or less, and 50 nanoseconds / shot or less.

In addition, when irradiation is performed using pulsed light having a relatively long wavelength (for example, a green laser having a wavelength of 532 nm), the number of irradiation times of the pulsed light is, for example, 5 times or more, 10 times or more, 25 times or more, or It can be 50 times or more and 300 times or less, 200 times or less, or 100 times or less. In this case, the irradiation energy of the pulsed light, for ^{example, 100mJ / (cm 2 · shot} ) ^{above, 300mJ / (cm 2 · shot} ) ^{above, 500mJ / (cm 2 · shot} ) above, 900 mJ / (cm ² · shot) or more, or 1300 mJ ^/ (a in cm 2 · shot) ^{above, 3000mJ / (cm 2 · shot} ) or ^{less, 2000mJ / (cm 2 · shot} ) or less, or 1500mJ ^/ (cm 2 · shot) below can do. Furthermore, in this case, the irradiation time of the pulsed light is, for example, 50 nanoseconds / shot or more, 100 nanoseconds / shot or more, or 150 nanoseconds / shot or more, and 300 nanoseconds / shot or less, 200 nanoseconds. / Shot or less, or 180 nanoseconds / shot or less.

  Here, if the number of times of light irradiation is too small, the energy per one pulse required to achieve the desired sintering is increased, and therefore the semiconductor silicon film may be damaged. Further, when the number of times of light irradiation is too small, the required processing time may become excessively long.

  In addition, selecting the number of pulsed light irradiations, irradiation energy, and irradiation time, particularly when the substrate has a polymer material, suppresses the deterioration of the polymer material due to heat, while sintering the silicon particles. It may be preferable to achieve.

(Irradiation atmosphere)
The light irradiation for sintering the silicon particles is preferably performed in a non-oxidizing atmosphere, for example, an atmosphere including hydrogen, a rare gas, nitrogen, and a combination thereof in order to prevent oxidation of the silicon particles. Here, examples of the rare gas include argon, helium, and neon. Note that it is preferable that the atmosphere contains hydrogen in order to suppress oxidation of silicon particles in the unsintered silicon film. In order to obtain a non-oxidizing atmosphere, the oxygen content of the atmosphere can be 1% by volume or less, 0.5% by volume or less, 0.1% by volume or less, or 0.01% by volume or less.

  The thickness of the semiconductor silicon film thus obtained is 50 nm or more, 100 nm or more, or 200 nm or more, and may be 2000 nm or less, 1000 nm or less, 500 nm or less, or 300 nm or less.

<< Semiconductor Device Manufacturing Method >>
The method of the present invention for manufacturing a semiconductor device, such as a field effect transistor (FET) or solar cell, comprises making a semiconductor stack by the method of the present invention. For example, the method of the present invention for manufacturing a field effect transistor can further include the steps of manufacturing a gate insulator, manufacturing source and drain electrodes, and the like. Further, for example, the method of the present invention for producing a solar cell can include a step of producing at least one of an N-type semiconductor and a P-type semiconductor by the method of the present invention, a step of forming a collecting electrode, and the like.

<< Semiconductor laminate and semiconductor device of the present invention >>
The semiconductor laminate of the present invention has a base material and a semiconductor silicon film laminated on the surface of the base material, and the semiconductor silicon film is made of a plurality of silicon particles sintered together. And the surface of a base material has big affinity with respect to molten silicon.

  Such a semiconductor laminate has a highly continuous semiconductor silicon film, which can provide favorable semiconductor characteristics.

  Such a semiconductor laminate can be produced by the method of the present invention for producing a semiconductor laminate.

  The semiconductor device of the present invention has the semiconductor laminate of the present invention. The semiconductor device of the present invention may be, for example, a field effect transistor or a solar cell.

  In addition, regarding the semiconductor laminate and the semiconductor device of the present invention, for materials having a high affinity for the substrate, silicon particles, molten silicon, etc., refer to the description relating to the method of the present invention for producing a semiconductor laminate. Can do.

<Example 1>
(Preparation of silicon particle dispersion)
Silicon particles were produced by a laser pyrolysis (LP) method using a CO ₂ laser using SiH ₄ gas as a raw material. The obtained silicon particles had an average primary particle size of about 7 nm. The silicon particles were ultrasonically dispersed in isopropyl alcohol (IPA) to obtain a silicon particle dispersion having a solid content concentration of 3 wt%.

(Preparation of base material)
A phosphorus (P) -doped silicon substrate (manufactured by Optstar, specific resistance of 0.005 Ωcm or less) was ultrasonically cleaned in acetone and isopropyl alcohol for 5 minutes each. Thereafter, a silicon nitride film having a film thickness of 500 nm was formed on the surface of the base material by chemical vapor deposition (CVD: Chemical Vapor Deposition).

(Application of silicon particle dispersion)
The silicon particle dispersion was applied to the substrate by dropping several drops of the silicon particle dispersion onto the substrate and spin coating at 500 rpm for 5 seconds and 4000 rpm for 10 seconds.

(Drying of silicon particle dispersion)
The substrate coated with the silicon particle dispersion is dried on a hot plate at 70 ° C. to remove isopropyl alcohol as a dispersion medium in the silicon particle dispersion, whereby silicon particles (average primary particle diameter of about An unsintered silicon particle film (film thickness 300 nm) including 7 nm) was formed.

(Light irradiation)
Next, this unsintered silicon particle film is irradiated with a YVO ₄ laser (wavelength 355 nm) using a laser beam irradiation apparatus (trade name Osprey 355-2-0, manufactured by Quantronix), and unsintered. The silicon particles in the silicon particle film were sintered, thereby producing a semiconductor silicon film. The laser irradiation conditions are an irradiation energy of 200 mJ / (cm ² · shot), 20 shots, and an irradiation time per shot of 30 nanoseconds.

The structure of the obtained laminate is shown in FIG. In FIG. 1, a silicon nitride film (Si ₃ N ₄ ) and a semiconductor silicon film (Si) are stacked in this order on a phosphorus (P) -doped silicon substrate (Si (P)). It is shown.

(Evaluation)
The surface of the produced semiconductor silicon film was observed by FE-SEM (field emission scanning electron microscope, S-5200 type, manufactured by Hitachi High-Technologies). The result is shown in FIG.

<Example 2>
The substrate was a silicon carbide single crystal substrate (manufactured by Optostar, substrate thickness 500 μm, specific resistance 0.01-0.03 Ωcm), and the laser irradiation energy was 300 mJ / (cm ² · shot). A semiconductor silicon film was fabricated in the same manner as in Example 1 except that.

  Similar to Example 1, the surface of the semiconductor silicon film was observed by FE-SEM. The result is shown in FIG.

<Example 3>
A field effect transistor (FET) having a bottom gate / top contact structure shown in FIG. 2 was manufactured, and its electrical characteristics were evaluated.

(Preparation of silicon particle dispersion)
A silicon particle dispersion was obtained in the same manner as in Example 1.

(Preparation of base material)
Phosphorus (P) -doped silicon substrate with a thermal silicon oxide film (SiO ₂ ) (thickness 1000 nm) (manufactured by Optstar, specific resistance 0.005 Ωcm or less), acetone, isopropyl alcohol, acid cleaning solution (trade name Frontier Clean) , Manufactured by Kanto Chemical Co., Ltd.) for 5 minutes each. Thereafter, a silicon nitride film having a film thickness of 60 nm was formed on the surface of the base material by chemical vapor deposition (CVD).

(Application and drying of silicon particle dispersion)
The silicon particle dispersion was applied and dried by the same method as in Example 1 except that the film thickness of the unsintered silicon film was 250 nm.

(Light irradiation)
Next, light irradiation was performed in the same manner as in Example 1 for sintering the unsintered silicon film.

(Formation of high-concentration phosphorus-doped silicon layer by P ion implantation)
In a commercially available ion implantation apparatus, an acceleration energy of 20 KeV, a phosphorus (P) dose of 4.0 × 10 ¹⁵ atms / cm ² , an implantation time of 5620 sec, a rotation speed of 0.6 rps, and a substrate temperature of room temperature, a semiconductor silicon film P ions were implanted to form a high concentration phosphorus-doped silicon layer. Thereafter, activation annealing was performed at 1000 ° C. for 3 minutes in a heating furnace in a nitrogen atmosphere.

(Al electrode formation by electron beam evaporation)
Thereafter, in a commercially available electron beam evaporation apparatus, an aluminum source electrode and drain electrode were formed on the high-concentration phosphorus-doped silicon layer. The film thickness of the aluminum source electrode and drain electrode was 100 nm.

The structure of the obtained FET (field effect transistor) is shown in FIG. In FIG. 2, a silicon nitride film (Si ₃ N ₄ ), a semiconductor silicon film (Si), a phosphorus (P) -doped silicon substrate (Si (P)) with a thermally oxidized silicon film (SiO ₂ ) film, In addition, the aluminum source electrode and the drain electrode (Al) are stacked in this order, and in the region below the source electrode and the drain electrode (Al), the semiconductor silicon film (Si) has a high concentration phosphorus ( It is shown that a P) doped silicon region (Si (P ⁺ )) is formed.

(Evaluation)
The electrical characteristics of the fabricated FET were evaluated using a semiconductor characteristic evaluation apparatus (manufactured by KEITHLEY, trade name 2636A type 2ch system source meter). In a state where a constant voltage of about 20 to 50 V is applied between the aluminum source electrode and the drain electrode, a variable voltage of −50 to 50 V is applied to the phosphorus (P) -doped silicon base material which is the gate, and the source electrode and the drain The response of the current flowing between the electrodes (drain current) to the gate voltage was examined. The measurement was performed 5 times. As a result, it was confirmed that the carrier mobility (average value) was 5.5 × 10 ⁻² cm ² / Vs.

  The transfer characteristic of this FET is shown in FIG. 4, and the output characteristic is shown in FIG.

<Comparative example 1>
A phosphorus (P) -doped silicon substrate with a thermally oxidized silicon film (SiO ₂ ) film (manufactured by Optstar, specific resistance of 0.005 Ωcm or less) was used as the substrate, and a silicon nitride film (Si ₃ N ₄ ) was used. A semiconductor silicon film was produced in the same manner as in Example 1 except that it was not used and the irradiation energy was changed from 200 mJ / (cm ² · shot) to 160 mJ / (cm ² · shot).

  Similar to Example 1, the surface of the semiconductor silicon film was observed by FE-SEM. The result is shown in FIG. Compared to FIGS. 3 (a) and 3 (b) for Examples 1 and 2, in FIG. 3 (c) for Comparative Example 1, although the irradiation energy is small, agglomeration of silicon particles proceeds and is coarse. It is understood that the semiconductor silicon film is discontinuous.

10 silicon particles 10a molten silicon particles 100 base material 100a base material surface (high affinity for molten silicon)
100b Substrate surface (low affinity for molten silicon)
120 Unsintered silicon particle film 130a Silicon film (present invention)
130b Silicon film (prior art)
200 Laser light

Claims (19)

A method for producing a semiconductor laminate having a substrate and a semiconductor silicon film laminated on the substrate,
(A) applying a silicon particle dispersion containing a dispersion medium and silicon particles dispersed in the dispersion medium on the surface of the substrate to form a silicon particle dispersion film;
(B) drying the silicon particle dispersion film to form an unsintered silicon film; and (c) irradiating the unsintered silicon film with light to form the unsintered silicon film in the unsintered silicon film. Sintering silicon particles, thereby forming a semiconductor silicon film;
And a contact angle of the molten silicon with respect to the surface of the base material is 70 degrees or less.   The method of claim 1, wherein the surface of the substrate is provided by a material selected from the group consisting of carbide, nitride, carbonitride, and combinations thereof.   The method of claim 2, wherein the surface of the substrate is provided by a material selected from the group consisting of silicon carbide, silicon nitride, silicon carbonitride, graphite, and combinations thereof.   The said base material has a base-material main body and a surface layer, and the said surface layer is made from the material whose contact angle by a molten silicon is 70 degrees or less, It is any one of Claims 1-3. the method of.   The method according to claim 1, wherein the entire substrate is made of the same material as the surface of the substrate.   The method as described in any one of Claims 1-5 whose average primary particle diameter of the said silicon particle is 100 nm or less.   The method according to claim 1, wherein the silicon particles are silicon particles obtained by a laser pyrolysis method.   The method according to claim 1, wherein the light irradiation is performed in a non-oxidizing atmosphere.   The method according to claim 1, wherein the light irradiation is performed using a laser.   The method according to claim 9, wherein the wavelength of the laser is 600 nm or less.   The method according to claim 1, wherein the light irradiation is performed using pulsed light.   The manufacturing method of a semiconductor device including making a semiconductor laminated body by the method as described in any one of Claims 1-11.   The semiconductor laminated body obtained by the method as described in any one of Claims 1-11.   A semiconductor device obtained by the method of claim 13. A substrate, and a semiconductor silicon film laminated on the surface of the substrate;
The semiconductor silicon film is made of a plurality of silicon particles sintered together, and the contact angle of the molten silicon with respect to the surface of the substrate is 70 degrees or less.
Semiconductor stack.   The semiconductor laminate according to claim 15, wherein the semiconductor silicon film has a thickness of 50 to 500 nm.   A semiconductor device comprising the semiconductor laminate according to claim 15. A method for producing a semiconductor laminate having a substrate and a semiconductor silicon film laminated on the substrate,
(A) applying a silicon particle dispersion containing a dispersion medium and silicon particles dispersed in the dispersion medium on the surface of the substrate to form a silicon particle dispersion film;
(B) drying the silicon particle dispersion film to form an unsintered silicon film; and (c) irradiating the unsintered silicon film with light to form the unsintered silicon film in the unsintered silicon film. Sintering silicon particles, thereby forming a semiconductor silicon film;
And the surface of the substrate is provided by a material selected from the group consisting of silicon carbide, silicon nitride, silicon carbonitride, graphite, and combinations thereof. A substrate, and a semiconductor silicon film laminated on the surface of the substrate;
The semiconductor silicon film is made of a plurality of silicon particles sintered together, and the surface of the substrate is made of silicon carbide, silicon nitride, silicon carbonitride, graphite, and combinations thereof. Provided by a material selected from the group,
Semiconductor stack.