JP4527090B2 - Manufacturing method of semiconductor substrate - Google Patents

Manufacturing method of semiconductor substrate Download PDF

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JP4527090B2
JP4527090B2 JP2006215122A JP2006215122A JP4527090B2 JP 4527090 B2 JP4527090 B2 JP 4527090B2 JP 2006215122 A JP2006215122 A JP 2006215122A JP 2006215122 A JP2006215122 A JP 2006215122A JP 4527090 B2 JP4527090 B2 JP 4527090B2
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semiconductor substrate
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純一 半那
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純一 半那
大日本印刷株式会社
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The present invention relates to a method of manufacturing a semiconductor substrate, more particularly to a method for producing a large area electronic group IV used in devices such as a semiconductor polycrystal obtained by forming on a substrate a semiconductor substrate.

  In the manufacture of Group IV polycrystalline semiconductor thin films for large-area electronic devices such as solar cells and thin film transistors, the development of low-temperature growth technology that enables the use of inexpensive low-melting-point materials such as glass is a major issue. . Up to now, polycrystalline thin films have been manufactured by thermal crystallization methods in which the corresponding group IV element amorphous film is thermally crystallized at a temperature of several hundred degrees C. or higher, and laser annealing methods in which crystallization is performed by laser irradiation. As described above, a method of crystallizing a previously deposited amorphous film or a material gas starting from a gas phase such as a thermal CVD method, a plasma CVD method, a photo CVD method, etc. Phase growth methods have been studied.

  However, the thermal crystallization method requires long-time heat treatment at a high temperature around 600 ° C., and the laser annealing method has a limited area that can be crystallized by a single laser irradiation. In addition to practical problems such as inability to ensure uniformity, it is pointed out that it is difficult to control the positive orientation of crystal grains that are useful for improving the characteristics.

  On the other hand, deposition by vapor deposition requires a high growth temperature of about 600 ° C. in the thermal CVD method using heat for decomposition of the source gas, and a low melting point substrate such as glass cannot be used. In the plasma CVD method using plasma for decomposing, the crystallinity non-uniformity in the film thickness direction is unavoidable, especially in the low temperature growth of 500 ° C. or less on an amorphous substrate such as glass at the initial stage of film deposition. In many cases, an amorphous phase is generated on a substrate, and there is a problem in that a film having high crystallinity needs to be deposited thickly.

  Furthermore, in the production of the conventional group IV polycrystalline semiconductor thin film, there has been a problem that a method for controlling the grain size control and crystal orientation which has a great influence on the material characteristics has not been established.

  Conventionally, in order to solve these problems, in the growth of a polycrystalline film, an amorphous layer containing zinc sulfide having a lattice constant substantially the same as that of Si and crystal grains formed by a plasma CVD method is used as an underlayer (nucleation generation). A method for promoting crystal growth by using it in a layer has been proposed. However, in the former method, since elements other than Group IV such as zinc and sulfur are used, there is a problem in application to an actual device. In the latter method, since the underlayer contains an amorphous phase, In order to obtain a high polycrystal, there is a problem that the method for forming a polycrystal layer is limited to a solid phase growth method or the like.

  On the other hand, in a method called centaxy, it has been reported that high quality and grain size control of a polycrystalline Si film can be realized by a combination of selective crystal nucleus formation and selective growth with Si. Since a high temperature of 900 ° C. or higher is required for the growth of the polycrystalline film, there is a problem that a low melting point substrate such as glass cannot be used.

The present invention provides a method for producing a semiconductor substrate that is excellent in crystallinity and can control the grain size and orientation of crystal grains by using a conventional low-temperature crystal growth technique in the production of group IV semiconductor polycrystals. The purpose is to do.

  As a result of research, the present inventor has found that in thermal CVD of germanium halide and silanes, at a low growth temperature of 550 ° C. or less, the substrate is directly formed without the formation of an amorphous layer at the initial stage of film growth. It has been found that crystal nuclei that cause crystal growth can be formed on the material, and that the formation density of the crystal nuclei can be controlled over a wide range by thermal CVD conditions. Based on this knowledge, in the manufacture of group IV polycrystalline semiconductor thin films, first, the crystal nuclei are formed on the substrate by the thermal CVD method, and then the conventional low-temperature crystal growth is performed using the crystal nuclei. By performing crystal growth using this technology, we have established a technology that enables easy and low-temperature production of polycrystalline thin films with controlled high crystallinity, crystal grain size, and orientation, which have been difficult in the past.

The method of manufacturing a semiconductor substrate according to claim 1 according to the present invention, by a thermal CVD method using germanium halide and silane as raw material at 550 ° C. temperature below amorphous, polycrystalline or metal substrates above, after forming nucleation density in the range of crystal nuclei 10 5 ~10 10 cm -2 of semiconductor material comprising a group IV element, the crystal nuclei by using as nuclei, IV group element on the crystal nuclei An amorphous phase of a semiconductor material containing is deposited, and the amorphous phase is crystallized by a solid phase growth method to form a polycrystal.

According to a second aspect of the present invention, in the method of manufacturing a semiconductor substrate according to the first aspect, the formation density of the crystal nuclei is controlled by changing pressure or time .

The invention according to claim 3 is the method of manufacturing a semiconductor substrate according to claim 1 or 2 , wherein the amorphous substrate is patterned by (1) glass, (2) metal or ITO conductive thin film. (3) a substrate obtained by laminating an amorphous thin film selected from silicon oxide and silicon nitride on a substrate, (4) silicon oxide on a substrate patterned with a conductive thin film of metal or ITO, It is any one selected from a base material on which an amorphous thin film selected from silicon nitride is laminated .

The invention according to claim 4 is the method for manufacturing a semiconductor substrate according to any one of claims 1 to 3, wherein the group IV element constituting the crystal nucleus is selected from Si, SiGe, and Ge. Features.

The invention according to claim 5 is the method for producing a semiconductor substrate according to claim 4 , wherein the crystal nucleus includes an impurity selected from P, As, Sb, and B.

The invention according to claim 6 is the method for manufacturing a semiconductor substrate according to any one of claims 1 to 5, wherein the group IV element constituting the polycrystal is selected from Si, SiGe, and Ge. Features.

The invention according to claim 7 is the method for producing a semiconductor substrate according to claim 6 , wherein the polycrystal includes an impurity selected from P, As, Sb, and B.

Invention of Claim 8 is a manufacturing method of the semiconductor base material of any one of Claims 1-7, The formation method of the said amorphous phase is CVD method, a vacuum evaporation method, or sputtering method. characterized in that there.

  That is, the present invention uses a thermal CVD method using germanium halide and silane as raw materials at a temperature of 550 ° C. or lower, and selects the growth conditions and nucleation time, thereby controlling the controlled density and orientation. Conventionally known SiGe or Ge crystal nuclei are formed on a substrate at a pressure of 10 torr or more and plasma CVD, photo CVD, or amorphous phase thermal crystallization is used as a nuclei. A method for producing a group IV semiconductor polycrystal, characterized by forming a polycrystal of a semiconductor by performing crystal growth using a low-temperature crystal growth technique for a group IV semiconductor thin film, and a semiconductor substrate (semiconductor polycrystal obtained) ).

  For the formation of crystal nuclei, it is important to use germanium halides such as germanium fluoride and germanium chloride and silane, disilane, or their halogen derivatives effective for reduction thereof. In this case, the source gas can be diluted with an inert gas such as He, Ar, or nitrogen or hydrogen. These selections can expand the range of nucleation conditions and density control. In addition, when crystal nuclei containing impurities such as P, As, Sb, and B are required for application, it is effective to add a gas containing these elements to the source gas.

  The crystal nucleus formation temperature is preferably in the range of 200 ° C. to 550 ° C. of the substrate temperature. If it is 200 ° C. or lower, the speed of the forming reaction is slow, and if it is 550 ° C. or higher, it is difficult to use a low-melting-point material such as glass for the substrate.

The formation density of crystal nuclei needs to be selected depending on the target device, and is generally selected from 10 3 to 10 14 cm −2 . More preferably, the case of producing a material for the vertical devices such as solar cells, typically nucleation density is preferably as small, also when applied to thin film transistors and the like are determined by the size of individual devices, 10 5 ~ 10 14 cm −2 is preferred.

  The shape of the crystal nuclei formed on the substrate is not necessarily limited to the shape in which the crystal nuclei are not necessarily isolated from each other on the substrate and may be continuously connected.

  A polycrystalline growth method using the formed crystal nucleus as a nucleus can be used for vapor phase growth methods such as thermal CVD method, plasma CVD method, and photo CVD method, but is not limited thereto. Instead, a solid phase growth method is used in which an amorphous phase of an IV semiconductor is deposited on the formed crystal nucleus by a plasma CVD method, a thermal CVD method, a vacuum evaporation method, a sputtering method, or the like, and is thermally crystallized. It is possible.

  By selecting the formation conditions of the initial crystal nuclei and the thickness of the formed initial crystal nuclei layer, the preferred orientation of the grown polycrystal is set so that, for example, (111), (110), (100) becomes dominant. Conditions can be set.

  The present invention forms crystal nuclei on a substrate at a low temperature of 550 ° C. or lower by a thermal CVD method, and uses this as a nucleus to perform crystal growth by using a low-temperature crystal technology of a group IV semiconductor, thereby producing crystallinity. Is an easy and low-temperature method for producing a polycrystalline semiconductor film, which opens up a way to control the crystal grain size and orientation, which has been difficult in the past. It is a very useful invention that brings about new developments in devices.

  Hereinafter, the semiconductor substrate of the present invention and the manufacturing method thereof will be described. The following examples illustrate the invention in detail, but are not limited thereto.

Example 1
Using SiO 2 formed on a Si wafer as a substrate, germanium fluoride and disilane were flowed in a reaction vessel of 2.7 sccm and 20 sccm, respectively, He for dilution was flowed into a 500 sccm reaction vessel, and the pressure was changed to 15 to 50 torr. When partial deposition is performed, about 10 5 to 10 6 cm −2 at 15 torr, about 10 7 to 10 8 cm −2 at 20 torr, about 10 8 to 10 9 cm −2 at 25 torr, and about 10 9 to 10 10 at 50 torr. Crystal nuclei were formed at a density of cm −2 . After crystal nuclei were formed on the substrate in advance under these conditions, a SiGe polycrystal having high crystallinity was obtained by lowering the growth temperature to 375 ° C. and continuing the growth. From the observation of the grown polycrystal with an electron microscope, it was confirmed that the smaller the density of crystal nuclei formed in the initial stage, the larger the crystal grain size.

(Example 2)
When a film was grown using a glass substrate under the same conditions as in Example 1, no significant difference was observed depending on the substrate, and a polycrystalline SiGe film with a controlled crystal grain size was obtained.

(Example 3)
Using SiO 2 formed on a Si wafer as a substrate, germanium fluoride and disilane were flowed in a reaction vessel of 2.7 sccm and 20 sccm, respectively, and He was diluted to 500 sccm for dilution, the pressure was fixed at 20 torr, and the growth time was 375 ° C. When deposition was performed instead, crystal nuclei of about 10 6 to 10 7 cm −2 were formed in 10 minutes and about 10 7 to 10 8 cm −2 in 20 minutes. After crystal nuclei were formed on the substrate in advance under these conditions, the reaction pressure was reduced to 10 torr and the growth was continued. As a result, a SiGe polycrystal having high crystallinity was obtained. It was confirmed by observation with an electron microscope that the crystal grain size of the obtained polycrystal was larger when nucleating for 10 minutes was larger than when nucleating for 20 minutes.

Example 4
After depositing germanium fluoride and disilane at 2.7 sccm and 20 sccm, respectively, He for dilution at 500 sccm reaction vessel and pressure of 10 torr at 450 ° C. for 60 seconds using glass as a substrate, source gas was once removed from the reaction vessel. After evacuation, the growth temperature was lowered to 375 ° C. and the film was grown for 1 minute. As a result, a SiGe film of about 0.1 μm was obtained. When the crystallinity was evaluated by a Raman spectrum, it was confirmed that the crystallinity was significantly improved by comparing the spectral intensity and the half-value width as compared with the film continuously grown at 450 ° C.

(Example 5)
After forming crystal nuclei on a glass substrate under the same conditions as in Example 1, silane-fluorinated silane-hydrogen was set to flow rates of 2 sccm, 98 sccm, and 50 sccm, respectively, and a glow discharge decomposition method was performed at a pressure of 1 torr. As a result of film growth at 400 ° C., a polycrystalline film in which almost no amorphous layer was found from the Raman spectrum was grown. From the observation of the grown film with an electron microscope, it was confirmed that the crystal grain size tends to increase as the density of crystal nuclei formed in the initial stage decreases.

(Example 6)
Crystal nuclei were formed on a glass substrate under the same conditions as in Example 1, and then a film was grown at 300 ° C. by an rf-glow discharge method using hydrogen diluted silane (2%). From the spectrum, a polycrystalline film with almost no amorphous layer was obtained.

(Example 7)
After forming crystal nuclei on a glass substrate under the same conditions as in Example 1, flow rate conditions of 25 sccm of silane and 25 sccm of fluorine (10% He dilution) were obtained by a film forming method utilizing a silane-fluorine chemical reaction. When a film was grown under a reaction pressure of 550 mtorr and 350 ° C., a polycrystalline film with extremely high crystallinity was grown. In the Raman spectrum, almost no amorphous layer was observed in the grown polycrystalline film, and it was revealed from the measurement of X-ray diffraction that the crystallinity was greatly improved. Further, it was recognized that the grain size tends to increase as the density of crystal nuclei formed in the initial stage decreases.

(Example 8)
After forming crystal nuclei on a glass substrate under the same conditions as in Example 1, an amorphous Si film was deposited at 100 ° C. by a silane glow discharge decomposition method at 0.5 ° C. After removing the hydrogen, a heat treatment was performed at 600 ° C. for 10 hours to obtain a polycrystalline film. From the measurement of X-ray diffraction, it was found that the orientation of the grown polycrystal was dominant in the orientation of the original crystal nuclei, and the size tended to increase as the initial nucleation density decreased.

Example 9
After forming crystal nuclei on the glass substrate under the same conditions as in Example 1, an amorphous Si film of 0.5 μm was deposited at 480 ° C. by thermal decomposition of disilane, followed by heat treatment at 600 ° C. for 10 hours. As a result, polycrystals with larger crystal grains grew with the film having a smaller grain size. From the measurement of X-ray diffraction, the orientation of the grown polycrystal was dominant in the orientation of the original crystal nucleus.

(Example 10)
After forming crystal nuclei on a glass substrate under the same conditions as in Example 1, an amorphous Si film was deposited by sputtering and then heat-treated at 600 ° C. for 10 hours. A polycrystalline film was obtained. As for the grain size, it was found that the film formed earlier with fewer crystal nuclei has larger crystal grains. From the measurement of X-ray diffraction, the orientation of the grown polycrystal was dominant in the orientation of the original crystal nucleus.

2 is an electron micrograph of crystal nuclei formed under the conditions shown in Example 1. FIG. In FIG. 1, (a) is the case where the reaction pressure is 15 torr (white line in the figure is 10 μm), (b) is the case where the reaction pressure is 20 torr (white line in the figure is 10 μm), (C) is the case where the reaction pressure is 25 torr (the white line in the figure is 1 μm), and (d) is the case where the reaction pressure is 50 torr (the white line in the figure is 1 μm). It is the figure which compared the crystallinity of the deposited SiGe deposited film when the crystal nucleus was formed in the deposition of the SiGe film by the thermal CVD method and when the formation of the crystal nucleus was not performed, according to the intensity of the Raman spectrum. In FIG. 2, (a) shows the Raman of the SiGe film deposited when nucleation was performed at 450 ° C. for 1 minute on a glass substrate by a germanium fluoride-disilane thermal CVD method and then deposited at 375 ° C. for 1 minute. (B) is a Raman spectrum of a SiGe film similarly deposited at 450 ° C. without nucleation. In the deposition of the SiGe film by thermal CVD method using germanium fluoride and disilane shown in Example 1, the nucleation was performed by selecting the formation conditions of the crystal nuclei, thereby controlling the orientation of the SiGe polycrystalline film. 2 is an X-ray diffraction spectrum showing an example. In FIG. 3, (a) is an X-ray diffraction spectrum of a SiGe film deposited at a reaction pressure of 10 torr and 425 ° C. without forming a crystal nucleus in advance, and (b) is a reaction pressure of 10 torr and 425 ° C. FIG. 4C is an X-ray diffraction spectrum of a SiGe film grown at 375 ° C. after preliminarily forming crystal nuclei for 1 minute, and (c) shows pre-formation of crystal nuclei at reaction pressure 20 torr and 375 ° C. for 5 minutes. 3 is an X-ray diffraction spectrum of a SiGe film grown at a reaction pressure of 10 torr and 375 ° C. FIG.

Claims (8)

  1. By a thermal CVD method using germanium halide and silane as raw material at 550 ° C. temperature below amorphous, on the polycrystalline or metal substrates, 105 to the crystal nuclei of semiconductor material comprising a group IV element After forming with a nucleation density in the range of 10 cm −2 ,
    Using the crystal nucleus as a nucleus , depositing an amorphous phase of a semiconductor material containing a group IV element on the crystal nucleus , and crystallizing the amorphous phase by a solid phase growth method to form a polycrystal. A method for producing a semiconductor substrate, which is characterized.
  2. The method for producing a semiconductor substrate according to claim 1, wherein the formation density of the crystal nuclei is controlled by changing pressure or time.
  3. The amorphous base material is (1) glass, (2) glass in which a conductive thin film of metal or ITO is patterned, and (3) an amorphous thin film selected from silicon oxide and silicon nitride is laminated on the base material. The substrate selected from (4), a substrate obtained by laminating an amorphous thin film selected from silicon oxide and silicon nitride on a substrate patterned with a conductive thin film of metal or ITO, A method for producing a semiconductor substrate according to 1 or 2.
  4. The method for producing a semiconductor substrate according to any one of claims 1 to 3 , wherein the group IV element constituting the crystal nucleus is selected from Si, SiGe, and Ge.
  5. The method for producing a semiconductor substrate according to claim 4 , wherein the crystal nucleus includes an impurity selected from P, As, Sb, and B.
  6. The method for producing a semiconductor substrate according to any one of claims 1 to 5, wherein a group IV element constituting the polycrystal is selected from Si, SiGe, and Ge.
  7. The method for producing a semiconductor substrate according to claim 6 , wherein the polycrystal includes an impurity selected from P, As, Sb, and B.
  8. The method for producing a semiconductor substrate according to claim 1, wherein the method for forming the amorphous phase is a CVD method, a vacuum deposition method, or a sputtering method.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0360026A (en) * 1989-07-27 1991-03-15 Sanyo Electric Co Ltd Manufacture of crystalline silicon film
JPH05315269A (en) * 1992-03-11 1993-11-26 Central Glass Co Ltd Forming method for thin film
JPH0766132A (en) * 1993-08-24 1995-03-10 Alcan Tec Kk Deposition of polycrystalline thin film
JPH08264440A (en) * 1995-03-25 1996-10-11 Junichi Hanna Manufacture of semiconductor substrate

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0360026A (en) * 1989-07-27 1991-03-15 Sanyo Electric Co Ltd Manufacture of crystalline silicon film
JPH05315269A (en) * 1992-03-11 1993-11-26 Central Glass Co Ltd Forming method for thin film
JPH0766132A (en) * 1993-08-24 1995-03-10 Alcan Tec Kk Deposition of polycrystalline thin film
JPH08264440A (en) * 1995-03-25 1996-10-11 Junichi Hanna Manufacture of semiconductor substrate

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