TWI555077B - A manufacturing method of a semiconductor device, a manufacturing apparatus for a semiconductor device, and a semiconductor device Body device, and transfer element - Google Patents

Description

Semiconductor device manufacturing method, semiconductor device manufacturing device, and semiconductor Body device and transfer component

The present invention relates to a method of manufacturing a semiconductor device, a device for manufacturing a semiconductor device, a semiconductor device, and a device for transfer.

Conventionally, in a crystalline solar cell, the planar surface of the substrate is deformed into a concavo-convex shape, that is, the so-called "light trap effect" is used to improve the energy conversion efficiency. This is because the light that is once reflected on the inclined surface of the uneven surface is also absorbed by the light on the inclined surface of the adjacent uneven surface as compared with the case where the surface of the substrate is flat, whereby the reflectance from the surface can be substantially reduced. As a result, since the total amount of incident light is increased, an increase in conversion efficiency is achieved.

In the method of forming the uneven structure, for example, a method of immersing a ruthenium substrate in a mixed aqueous solution of an oxidizing agent containing a metal ion of a catalyst and hydrofluoric acid has been proposed (Patent Document 1). Accordingly, a technique for forming a porous tantalum layer on the surface of the substrate is disclosed.

<Previous Technical Literature>

<Patent Document 1> JP-A-2005-183505

However, the controllability of the above-described method for forming the uneven structure with respect to the formation of the uneven shape is still not sufficient. Specifically, in the above method, first, it is considered that since the metal on the surface of the ruthenium substrate is precipitated from the surface of the ruthenium substrate, the metal can function as a decomposition catalyst. As a result, since the precipitation position or distribution of the metal cannot be controlled freely, it is extremely difficult to ensure the uniformity of the size or distribution of the formed irregularities, and the reproducibility of such characteristics is also insufficient. Furthermore, it is difficult to remove the metal after the surface uneven structure is produced.

In addition, research and development based on the industrial and even mass production considerations for the specific means for forming such uniform irregularities will be able to meet the needs of the industry.

In order to solve at least one of the above problems, the present invention achieves a surface having an uneven shape which is excellent in industriality and mass productivity, and excellent in uniformity and reproducibility on a semiconductor substrate. As a result, the present invention has a significant contribution to the stabilization of high performance of various semiconductor devices represented by solar cells and the realization of industrialization thereof.

A method of manufacturing a semiconductor device according to the present invention includes supplying a processing liquid that oxidizes and dissolves a semiconductor substrate to a surface of the semiconductor substrate; and designing a grid-shaped transfer member having a catalyst material to be in contact or close to The arrangement process of the arrangement state of the surface of the semiconductor substrate; and the formation process of the surface of the semiconductor substrate having the uneven surface by the supply process and the arrangement described above.

According to the method of manufacturing a semiconductor device, since the unevenness of the semiconductor substrate to be processed is formed in accordance with the mesh shape of the transfer element, the mesh shape of the transfer element can be used as a model or a film. A semiconductor device having a semiconductor substrate having irregularities reflected therefrom is obtained. In other words, it is not a semiconductor substrate which is arbitrarily high in the past, in other words, has low reproducibility, but is formed at a stage of the transfer element, and can be stably produced by forming a suitable mesh shape in advance. A semiconductor device of a semiconductor substrate having a predetermined level of unevenness.

Another method of manufacturing a semiconductor device according to the present invention includes supplying a processing liquid for oxidizing and dissolving a semiconductor substrate to a surface of the semiconductor substrate; and transferring the catalyst material on or above the surface on which the unevenness is formed The element is disposed so as to be in contact with or close to the arrangement state of the surface of the semiconductor substrate; and the unevenness forming process of forming the surface of the semiconductor substrate having the uneven surface by the supply process and the arrangement described above.

According to the method of manufacturing a semiconductor device, the unevenness of the semiconductor substrate to be processed is formed in accordance with the uneven shape of the transfer element. Therefore, the uneven shape of the transfer element can be obtained as a model or a film. A semiconductor device having a semiconductor substrate which is reflected by the unevenness. In other words, it is not a semiconductor substrate which is arbitrarily high in the past, in other words, has low reproducibility, but is formed at a stage of the transfer element, and can be stably produced by forming a suitable uneven shape in advance. A semiconductor device of a semiconductor substrate having a predetermined uneven shape.

Further, the apparatus for manufacturing a semiconductor device according to the present invention includes a supply device that supplies a processing liquid that oxidizes and dissolves the semiconductor substrate to the surface of the semiconductor substrate, and a grid-shaped transfer element having a catalyst material is disposed. A configuration device that contacts or approaches the surface of the semiconductor substrate.

According to the manufacturing apparatus of the semiconductor device, since the unevenness of the semiconductor substrate to be processed is formed in accordance with the mesh shape of the transfer element, the mesh shape of the transfer element can be used as a model or a film. A semiconductor device having a semiconductor substrate having irregularities reflected therefrom is manufactured. In other words, it is not a semiconductor substrate which is arbitrarily high in the past, in other words, has low reproducibility, but is formed at a stage of the transfer element, and can be stably produced by forming a suitable mesh shape in advance. A semiconductor device of a semiconductor substrate having a predetermined level of unevenness.

Further, another manufacturing apparatus of a semiconductor device of the present invention includes a supply device that supplies a processing liquid that oxidizes and dissolves a semiconductor substrate to a surface of the semiconductor substrate; and a catalyst material that is located on or above the surface on which the unevenness is formed or The transfer element is arranged to contact or approach the arrangement of the surface of the semiconductor substrate.

According to the manufacturing apparatus of the semiconductor device, since the unevenness of the semiconductor substrate to be processed is formed in accordance with the uneven shape of the transfer element, the uneven shape of the transfer element can be manufactured as a mold or a film. A semiconductor device having a semiconductor substrate which is reflected by the unevenness. In other words, it is not a semiconductor substrate which is arbitrarily high in the past, in other words, has low reproducibility, but is formed at a stage of the transfer element, and can be stably produced by forming a suitable uneven shape in advance. A semiconductor device of a semiconductor substrate having a predetermined uneven shape.

Further, the transfer element of the present invention is a mesh-like element having a catalyst material, and the catalyst medium is disposed in a state in which a treatment liquid having oxidizing property and solubility is present on the surface of the semiconductor substrate. The surface of the semiconductor substrate is brought into contact or approached, whereby the surface is deformed into a concavo-convex shape.

According to the transfer element, the unevenness of the semiconductor substrate to be processed is formed in accordance with the mesh structure of the transfer element. Therefore, the mesh structure of the transfer element can be stabilized as a model or a film. A semiconductor substrate having irregularities reflected by the ground is supplied.

Further, another transfer member of the present invention has a catalyst material on or above the surface on which the unevenness is formed, and in a state in which a treatment liquid having oxidizing property and solubility is present on the surface of the semiconductor substrate, The catalyst material is configured to contact or approach the surface of the semiconductor substrate, thereby deforming the surface into a concavo-convex shape.

According to the transfer element, the unevenness of the semiconductor substrate to be processed is formed in accordance with the uneven shape of the transfer element. Therefore, the uneven shape of the transfer element can be stably supplied as a mold or a film. A semiconductor substrate having irregularities reflected by the semiconductor substrate.

Further, in the semiconductor device of the present invention, the processing liquid that oxidizes and dissolves the semiconductor substrate is introduced onto the surface of the semiconductor substrate, and the grid-like transfer member having the catalyst material is placed in contact or close to the In the surface state, the surface on which the electrode is not formed has a porous uneven shape formed in the above state.

According to the semiconductor device, since the unevenness of the semiconductor substrate to be processed is formed in accordance with the mesh shape of the transfer element, the mesh shape of the transfer element can be made to be reflected as a model or a film. A semiconductor device of a semiconductor substrate having irregularities. In other words, it is not a semiconductor substrate which is arbitrarily high in the past, in other words, has low reproducibility, but is formed at a stage of the transfer element, and a predetermined mesh shape is formed in advance to obtain a certain level. A semiconductor device of a semiconductor substrate having an uneven shape.

Further, in the above-described invention, the transfer substrate is used for the semiconductor substrate to be processed, and the treatment liquid having oxidizing property and solubility is applied to form irregularities on the surface of the semiconductor substrate. A material having resistance (represented by etching resistance or insolubility) is preferred. Although it is not particularly limited, a crystalline semiconductor substrate or an element having a mesh structure can be used for the transfer element. Further, the unevenness in the transfer element is not limited to the case where it is formed by wet chemical etching as described above. For example, an isotropic or anisotropic dry etching using semiconductor technology or microelectromechanical system (MEMS) technology, or a fine uneven shape formed by a nanoimprint method can also be applied.

Further, in each of the above inventions, the mesh element is not limited to the case where the vertical line and the horizontal line represented by Fig. 9 are formed to intersect each other (for example, in a mesh shape). For example, there is only a vertical line, or a shape or a structure with only a horizontal line; or a part of the field is only a vertical line or a horizontal line, and other fields are shapes or structures in which the vertical line and the horizontal line intersect each other, and are included in the net. In the category of lattice elements.

Further, the inventors assumed the formation mechanism of the unevenness of the semiconductor substrate as follows. First, when the concave-convex surface of the surface of the transfer member or the catalyst material present on the mesh structure is brought into contact with the surface of the semiconductor substrate, the contact medium acts as a cathode for the electrochemical reaction, and the surface of the catalytic material The decomposition reaction of the oxidant occurs. On the other hand, the anodic reaction occurs on the surface of the crucible. In the case of a highly probable anode reaction, the following reaction can be considered.

<Chemical 1> Si+6HF+2h → H ₂ SiF ₆ +H ₂ +2H ⁺

In the case of the above-described anode reaction, for example, in the case of using the above-described grid-like transfer member, a porous (porous) crucible formed by dissolving the surface of the crucible can be considered. More specifically, the inventors of the present invention considered that hydrogen ions (H ⁺ ) are generated by the above reaction, so that the pH is increased, that is, the balance is shifted to the right side due to alkalinity, so that the porous state of the ruthenium is promoted. Form a reaction. That is, the formation reaction of the porous form can be promoted by the addition of a base. Further, when the catalyst acts on the surface of the semiconductor substrate as a decomposition catalyst of the oxidizing agent in the treatment liquid, the atomic oxygen generated by the oxidizing agent thereby oxidizes the surface of the semiconductor substrate. As such, the oxidized portion will dissolve the oxide layer with a solvating agent, thereby substantially etching the semiconductor surface. Further, the oxidation of the surface of the semiconductor substrate and the dissolution in the treatment liquid are repeated, thereby reflecting the approximate surface shape of the transfer member, in other words, the shape of the transfer member can be reversed by transfer. Concave shape. Therefore, in the above inventions, the catalyst material is not particularly limited as long as it acts on the decomposition catalyst which can act as an oxidizing agent in the treatment liquid. As must be mentioned, a preferred representative example of the catalyst is an alloy group comprising platinum (Pt), silver (Ag), palladium (Pd), gold (Au), rhodium (Rh), and such metals. At least one selected from the group.

In the present application, the term "the transfer device has a catalytic material" means a state in which a film or layer of a catalyst material is formed on the surface of the transfer member; and on the surface of the transfer member. The state in which the particulate or island-like catalyst is adhered to the container is included, and the catalyst material on the transfer element is used as a state in which the catalyst exhibits its function or performance. In addition, the "transfer element has a catalyst material" means that the transfer element itself may be formed of only a catalyst material even if it may contain an unavoidable impurity. Further, such a catalyst material is a film formed by a known sputtering method, a vapor deposited film formed by chemical vapor deposition (CVD), or a film formed by plating. A representative aspect, but not limited to these membranes.

According to the method of manufacturing a semiconductor device of the present invention, the unevenness of the semiconductor substrate to be processed is formed in accordance with the uneven shape or the mesh shape of the transfer element, so that the uneven shape or the mesh of the transfer member is formed. The lattice shape is used as a model or a film tool to obtain a semiconductor device having a semiconductor substrate having irregularities reflected therefrom. In other words, it is not a semiconductor substrate which is arbitrarily high in the past, in other words, has low reproducibility, but can be stably manufactured by forming a suitable uneven shape or mesh shape in advance at the stage of the transfer element. A semiconductor device having a semiconductor substrate having a predetermined level of irregularities.

Further, according to the apparatus for manufacturing a semiconductor device of the present invention, the unevenness of the semiconductor substrate to be processed is formed in accordance with the uneven shape or the mesh shape of the transfer element, so that the uneven shape of the transfer member is formed. Alternatively, the mesh shape can be used as a model or a film to manufacture a semiconductor device having a semiconductor substrate having irregularities reflected therefrom. In other words, it is not a semiconductor substrate which is arbitrarily high in the past, in other words, has low reproducibility, but can be stably manufactured by forming a suitable uneven shape or mesh shape in advance at the stage of the transfer element. A semiconductor device having a semiconductor substrate having a predetermined level of irregularities.

Further, according to the transfer element of the present invention, the unevenness of the semiconductor substrate to be processed is formed in accordance with the uneven shape or the mesh structure of the transfer element, so that the uneven shape of the transfer member or The mesh structure can be stably supplied as a mold or a film to a semiconductor substrate having irregularities reflected therefrom.

10,10a‧‧‧Transfer components

10b‧‧‧Grid-like transfer components

11‧‧‧N-type germanium substrate that has been treated with a mixed solution

12,22,22a‧‧‧ convex or concave surface

13‧‧‧Oxide film

15‧‧‧ nitride film

17‧‧‧Touch media

19‧‧‧Processing fluid

20,20a‧‧‧Processing substrate

40‧‧‧Processing tank

42‧‧‧Holding

30‧‧‧ Polycrystalline Substrate

31‧‧‧i type a-Si layer

32‧‧‧p ⁺ type a-Si layer

34‧‧‧Surface electrode layer

36‧‧‧Back electrode layer

50,51,52‧‧‧Manufacturing device for semiconductor devices

55, 56‧‧‧ supply device

57a, 57b, 57c, 57d‧‧‧ Roller

59‧‧‧Configure device

100‧‧‧Semiconductor device (solar cell)

Fig. 1 is a SEM (scanning electron microscope) photograph of a part of the surface of the manufacturing process of the transfer element in the first embodiment of the present invention.

Fig. 2A is a schematic cross-sectional view showing a process of a method for producing a transfer member according to the first embodiment of the present invention.

Fig. 2B is a schematic cross-sectional view showing a process of a method for producing a transfer member in the first embodiment of the present invention.

2C is a schematic cross-sectional view showing a process of a method for producing a transfer member in the first embodiment of the present invention.

Fig. 2D is a schematic cross-sectional view showing a process of a method for producing a transfer member according to the first embodiment of the present invention.

FIG. 2E is a schematic view showing a configuration of a main part of a manufacturing apparatus of a semiconductor device according to the first to fourth embodiments of the present invention.

FIG. 2F is a schematic cross-sectional view showing a transfer process performed on the substrate to be processed in the first embodiment of the present invention.

FIG. 2G is a schematic cross-sectional view showing the substrate to be processed after the transfer process in the first embodiment of the present invention.

Fig. 3 is a SEM photograph of the surface of the substrate to be processed in the first embodiment of the present invention.

Fig. 4 is a schematic cross-sectional view showing a substrate to be processed after a transfer process in a modification (1) of the first embodiment of the present invention.

Fig. 5 is a SEM photograph of the surface of the substrate to be processed in the second embodiment of the present invention.

Fig. 6 is a SEM photograph of the surface of the substrate to be processed in the third embodiment of the present invention.

Fig. 7 is a graph showing the spectral reflectance characteristics of the surface of the substrate to be processed in the third embodiment of the present invention.

Fig. 8 is a schematic cross-sectional view showing the main part of a solar cell according to a fourth embodiment of the present invention.

Fig. 9 is a perspective view showing the appearance of a grid-like transfer member in a fifth embodiment of the invention.

Fig. 10 is an optical micrograph (planar photograph) of the surface of the substrate to be processed in the fifth embodiment of the present invention.

Fig. 11A is a plan view showing a measurement target portion taken by a laser common-rail focal length microscope according to a fifth embodiment of the present invention.

Fig. 11B is a cross-sectional view showing the cross-sectional profile of the measurement target portion (X-X) in Fig. 11A.

FIG. 12 is a schematic view showing a configuration of a main part of a manufacturing apparatus of a semiconductor device according to a sixth embodiment of the present invention.

Fig. 13 is an explanatory view showing a state after the roller is disposed (during processing) with respect to the substrate to be processed in the sixth embodiment of the present invention.

Fig. 14A is an optical micrograph (planar photograph) of the surface of the substrate to be processed which is processed at 60 ° C in the sixth embodiment of the present invention.

Fig. 14B is an optical microscopic photograph of a cross section of the vicinity of the surface of the substrate to be processed which is processed at 60 °C in the sixth embodiment of the present invention.

Fig. 15 is a graph showing the reflectance of the surface of the substrate to be processed which is processed at 60 ° C in the sixth embodiment of the present invention.

Fig. 16 is a map showing the results of measurement of the lifetime of the substrate to be processed in the sixth embodiment of the present invention.

Fig. 17 is an optical micrograph (planar photograph) of the surface of the substrate to be processed in a modification (1) of the sixth embodiment of the present invention.

Fig. 18 is a graph showing the reflectance of the surface of the substrate to be processed in the modification (1) of the sixth embodiment of the present invention.

Fig. 19 is an optical microscopic photograph (planar photograph) of the surface of the substrate to be processed in a modification (2) of the sixth embodiment of the present invention.

Fig. 20 is a schematic view showing the configuration of a main part of a manufacturing apparatus of a semiconductor device according to a modification (3) of the sixth embodiment of the present invention.

21A is a cross-sectional view showing another roller and a mesh-shaped transfer element in a sixth embodiment of the present invention.

21B is a cross-sectional view showing another roller and a mesh-shaped transfer element in the sixth embodiment of the present invention.

21C is a cross-sectional view showing another roller and a mesh-shaped transfer element in the sixth embodiment of the present invention.

Next, embodiments of the present invention will be described in detail with reference to the accompanying drawings. Further, in the description of the drawings, the common portions will be denoted by the common reference numerals unless otherwise specified. Further, the elements of the present embodiment in the drawings are not always drawn with a reduction ratio of each other.

<First Embodiment>

In the present embodiment, first, a surface of a semiconductor substrate (a substrate to be processed (hereinafter referred to as a "substrate to be processed") to be used in a semiconductor device (a solar cell in the present embodiment) is formed into a concavo-convex shape. A method of manufacturing the transfer element 10 will be described. Fig. 1 is a scanning electron microscope (hereinafter referred to as SEM) photograph of a part of the surface of the manufacturing process of the transfer element in the embodiment. 2A to 2D are schematic cross-sectional views showing a process of the method of manufacturing the transfer member 10 of the embodiment. In addition, FIG. 2F is a schematic cross-sectional view for explaining a transfer process performed on the substrate to be processed in the embodiment. Fig. 2G is a schematic cross-sectional view showing the substrate to be processed after the transfer process in the embodiment.

In the production of the transfer element 10, a single crystal n-type ruthenium (100) (resistivity: 1 to 20 Ωcm) substrate subjected to surface cleaning treatment by a so-called RCA cleaning method was initially used, and the molar concentration was 0.25. A mixed aqueous solution of mol/dm ³ of sodium hydroxide (NaOH) and a molar concentration of 0.6 mol/dm ³ of 2-propanol was immersed for 20 minutes. Fig. 1 is a SEM photograph of the surface of the n-type ruthenium substrate 11 after the above-described manufacturing process, and Fig. 2A is a cross-sectional structural view schematically showing the first diagram. As shown in Fig. 1, a pyramid-shaped uneven surface 12 having a high uniformity can be formed, that is, a surface on which a embossed structure can be formed. According to the experiments of the present inventors, the single crystal germanium (Si-(100)) was immersed in an aqueous NaOH solution containing 2-propanol and having a molar concentration of about 0.01 mol/dm ³ to 5 mol/dm ³ from 10 to 30. In minutes, that is, by performing so-called anisotropic alkali etching, the reflectance of incident light (light below the infrared wavelength) in the surface of the substrate can be reduced to be significantly lower than that of the substrate surface which is only flat or planar.

Next, as shown in FIG. 2B, a thin oxide film (SiO ₂ ) 13 is formed on the surface of the n-type germanium substrate 11. The oxide film 13 of the present embodiment is formed by a wet oxidation method. The thickness of the oxide film 13 is several nanometers (mm) to several hundred nanometers (nm). This oxide film 13 serves as an anti-stripping layer for improving adhesion of a catalyst material to be described later to the surface of the n-type germanium substrate 11. Further, regarding the formation of the oxide film 13, in addition to the above wet oxidation method, any of a usual thermal oxidation method, a CVD deposition method, or a chemical oxide film formation method can be applied. Further, even if the thickness of the oxide film 13 is 1 μm or less, a film having high stability can be formed.

In the present embodiment, as shown in Fig. 2C, a tantalum nitride (Si ₃ N ₄ ) film 15 as an interlayer film is further formed on the oxide film 13. Here, the tantalum nitride film 15 of the present embodiment is formed by a deposition method called a cat-CVD method. The specific condition is that the pressure is 1 Pa. Further, regarding the flow rate, nitrogen (N ₂ ) was 0.6 sccm, and argon (Ar) was 0.4 sccm. Under the foregoing conditions, a tantalum nitride film 15 having a thickness of about 1 μm was formed by setting the deposition time to 2 hours. Further, in the method for producing the tantalum nitride film 15, a vacuum CVD method and a sputtering method may be applied in addition to the cat-CVD method. When the reduced pressure CVD method is employed, the oxide film 13 becomes unnecessary because of the high adsorptivity between the tantalum nitride film and the n-type germanium substrate 11.

Incidentally, the tantalum nitride film 15 functions as a protective film of the n-type germanium substrate 11 in the transfer element 10 or as a water-impermeable layer with respect to a processing liquid to be described later, that is, as a function The middle layer. Therefore, the tantalum nitride film 15 also functions as an anti-stripping layer of the catalyst material 17 to be described later. In the present embodiment, as described above, the two layers of the laminated oxide film 13 and the tantalum nitride film 15 are used for transfer prevention in order to prevent the peeling of the catalyst material 17 and improve the resistance to the processing liquid to be described later. The stability and reliability of the component 10 contribute greatly.

Next, as shown in FIG. 2D, in the present embodiment, a platinum (Pt) film as the catalyst material 17 is formed on the tantalum nitride film 15 by an electron beam (EB) vapor deposition method. The film thickness of the platinum film of this embodiment is about 50 to 100 nm. At this time, the adhesion of the platinum film is enhanced by heating the n-type germanium substrate 11 to 350 °C. Further, in order to further enhance the adhesion to the n-type ruthenium substrate 11 of the platinum film, it is preferable to carry out heat treatment at several hundred ° C in the inert gas after film formation. Here, in the present embodiment, a platinum (Pt) film is formed by an electron beam (EB) vapor deposition method, but a vacuum vapor deposition method or a sputtering method may be used instead of the electron beam (EB) vapor deposition method.

Then, the n-type ruthenium substrate 11 on which the film of the catalyst material 17 is formed is used as the transfer element 10 on the pyramid-shaped uneven surface 12, and the uneven shape of the semiconductor substrate to be processed is formed. FIG. 2E is a schematic view showing a configuration of a main part of the manufacturing apparatus 50 of the semiconductor device according to the embodiment. The processing target substrate 20 of the present embodiment is a single crystal germanium (100) substrate of a semiconductor substrate.

In the present embodiment, the pyramidal uneven surface 12 is placed facing the substrate 20 to be processed, and the transfer element 10 having the catalyst member 17 is placed in contact with or close to the substrate 20 to be processed. Configure the device. Further, in order to avoid contamination of the surface of the substrate 20 to be processed, the top portion of the catalyst material 17 on the surface of the platinum film is previously subjected to a surface cleaning treatment by an RCA cleaning method.

Then, a mixed aqueous solution of hydrofluoric acid (HF) as a solvent and hydrogen peroxide water (H ₂ O ₂ ) as an oxidizing agent is used as the treatment liquid 19, and is supplied to the surface of the substrate 20 to be processed and the catalyst 17 Between the platinum films (Fig. 2F). In the present embodiment, as shown in FIG. 2E, the transfer member 42 and the processing target substrate 20 disposed to face each other are immersed in the processing device as the processing liquid supply device. The treatment liquid 19 in the tank 40 is thereby subjected to the aforementioned treatment. Further, more specifically, the treatment liquid 19 is a mixed aqueous solution of hydrofluoric acid (HF) 5.3 M and hydrogen peroxide water (H ₂ O ₂ ) 1.8 M (water 1 dm ³ contains HF 5.3 mol and H ₂ O ₂ 1.8 mol).

As a result of observing the surface of the substrate 20 to be processed, the surface of the substrate 20 to be processed was observed as shown in FIG. 2G, and the uneven surface 22 on the surface of the substrate 20 to be processed was confirmed. Fig. 3 is a SEM photograph of the surface of the substrate 20 to be processed obtained in the present embodiment. Interestingly, when the first drawing and the third drawing are compared, the convex-concave surface of the surface of the transfer element 10 of the first drawing is a convex-concave surface having a convex-concave opposite shape in the third drawing. It can be seen that the reverse pyramid structure is transferred to almost the same shape. This is considered to be because the etching of the processing target substrate 20 is performed from the top of the convex portion of the surface of the transfer member 10 having the insoluble precursor of the uneven surface 12, and sequentially along the convex shape toward the side slope. . Therefore, the platinum surface of the catalyst member 17 on the surface of the transfer member 10 is brought into contact with or as close as possible to the surface of the substrate 20 to be processed, and the transfer member 10 is pressed to the substrate 20 to be processed as required. The pressure on the surface is better. However, the convex-concave surface 12 of the surface of the transfer element 10 is in close contact with the surface of the substrate 20 to be processed (so-called transfer surface), and the processing liquid 19 therebetween is removed, and etching of the substrate 20 to be processed has to be avoided. What does not happen. Therefore, in order to constantly maintain the supply of the processing liquid 19 at the time of pressing the transfer element 10, it is sufficient to set an appropriate contact or approach condition based on experience. Further, in the present embodiment, although the immersion time of the treatment liquid 19 was 2 hours, the inventors have confirmed that even if the immersion time is several minutes to 30 minutes, an equal surface shape can be formed.

<Modification (1) of the first embodiment>

Incidentally, in the present embodiment, the oxide film (SiO ₂ ) 13 and the tantalum nitride (Si ₃ N ₄ ) film 15 are formed on the surface of the n-type germanium substrate 11, but the first embodiment is not limited to the laminated structure. .

For example, FIG. 4 is a schematic cross-sectional view showing the substrate 20a to be processed after the transfer process in the embodiment. As shown in Fig. 4, the transfer element 10a of the present embodiment is different from the transfer element 10 of the first embodiment, and the oxide film 13 is not formed. Therefore, on the surface of the n-type germanium substrate 11, the tantalum nitride (Si ₃ N ₄ ) film 15 is formed by the same means as the film forming method of the first embodiment.

Even in such a transfer element 10a, at least some of the effects of the first embodiment can be exhibited. In other words, the surface of the substrate to be processed 20a roughly reflects the shape of the surface of the transfer element 10a, in other words, the shape of the surface of the transfer element 10a is transferred, and the uneven surface 22a is formed.

<Modification (2) of First Embodiment>

In addition to the modification (1) of the first embodiment, for example, even if an oxide film (SiO ₂ ) 13 is formed on the surface of the n-type germanium substrate 11, or even on the surface of the n-type germanium substrate 11, It is also possible to exhibit at least a part of the effects of the first embodiment when the catalyst medium 17 is disposed. However, from the viewpoint of preventing the contact of the catalyst material 17 from the n-type germanium substrate 11 and the dissolution of the n-type germanium substrate 11 itself, the direct contact with the catalyst material 17 on the surface of the n-type germanium substrate 11 is achieved. The other two aspects are preferable, and the structure in which the oxide film (SiO ₂ ) 13 and the tantalum nitride (Si ₃ N ₄ ) film 15 are formed as in the first embodiment is preferable.

<Second embodiment>

In the present embodiment, the formation of the uneven surface of the substrate to be processed is the same as that of the transfer member 10 of the first embodiment, except that the substrate 20 to be processed in the first embodiment is a single crystal germanium (111) substrate. The manufacturing method of the target substrate 20 is the same. Therefore, the description overlapping with the first embodiment can be omitted.

Fig. 5 is a SEM photograph of the surface of the substrate to be processed in the present embodiment. As shown in FIG. 5, although the depth of the surface of the substrate 20 to be processed is slightly different between the respective irregularities, the uneven surface of the transfer element 10 is almost reflected, in other words, the transfer member is known. The embossed structure transferred by the concave and convex surface of 10, that is, the convex and concave surfaces are opposite, that is, the so-called reverse pyramid The face is formed. Therefore, it was confirmed that transfer was not performed depending on the crystal orientation of the single crystal germanium substrate.

<Third embodiment>

In the present embodiment, the processing target substrate 20 is a poly-Si substrate, and the processing time of the processing liquid 19 in the first embodiment is different from that in the first embodiment. The manufacturing method of the target substrate 20 is the same. Therefore, the description overlapping with the first embodiment can be omitted.

In the present embodiment, a poly-Si substrate as the substrate 20 to be processed is immersed in the treatment liquid 19 for 4 hours. Fig. 6 is a SEM photograph of the surface of the substrate 20 to be processed in the present embodiment. As shown in Fig. 6, it is observed that the smoothness of the substrate 20 to be processed is slightly different from that of the unevenness, but a transfer structure similar to the uneven structure of the transfer member 10 is formed. The surface of the grain structure (inverse pyramid). Here, the formation time of the unevenness on the surface of the substrate 20 to be processed can be greatly shortened by the concentration control of hydrofluoric acid and hydrogen peroxide water in the treatment liquid 19, and the like. Specifically, for example, by adjusting the concentration of hydrogen peroxide, the processing time by the treatment liquid 19 can be greatly shortened.

Further, Fig. 7 is a graph showing the spectral reflectance characteristics of the surface of the polycrystalline silicon substrate in the present embodiment. The solid line in the figure indicates the result of the surface of the substrate 20 to be processed after the processing in the present embodiment, and the broken line indicates the result of the surface of the substrate 20 to be processed before the processing. As is clear from Fig. 7, it is confirmed that the surface of the substrate 20 to be processed by the process of the present embodiment has a large reflectance at all wavelengths from 300 nm to 800 nm as compared with the untreated surface.

<Fourth embodiment>

Fig. 8 is a schematic cross-sectional view showing a main part of a solar cell 100 manufactured by using the polycrystalline germanium substrate of the present embodiment.

In the present embodiment, a known film formation technique (for example, a plasma vapor deposition method (PCVD) method) is employed on the n-type polycrystalline silicon substrate 30 having the uneven surface formed by the third embodiment. The i-type a-Si layer 31 and the p ⁺ -type a-Si layer 32 are laminated. Then, in the ITO film which is a transparent conductive film, the surface electrode layer 34 is formed on the p ⁺ -type a-Si layer 32 by, for example, a known sputtering method. Further, on the reverse surface of the polycrystalline silicon substrate 30, the n ⁺ -type a-Si layer as the back electrode layer 36 is formed by a known film formation technique (for example, a plasma vapor deposition (PCVD) method).

As shown in Fig. 8, a polycrystalline silicon substrate 30 having a surface formed by performing the above-described third embodiment is used to fabricate the solar cell 100, whereby in the interior of the solar cell 100, incident light is realized. The antireflection effect produces a decrease in light reflectance and an increase in photocurrent.

In addition, in the case of any of the above-described embodiments, the mechanism for performing the reaction by the treatment liquid 19 is assumed to be as follows when referring to FIGS. 2E and 2F. First, in the treatment liquid 19 containing hydrofluoric acid (aqueous HF solution) and hydrogen peroxide water (aqueous solution of H ₂ O ₂ ) as an oxidizing agent, it can be used as a catalytic material on or above the transfer member 10. The platinum film of 17 acts on the surface of the substrate 20 to be treated as a decomposition catalyst for the oxidizing agent. As a result, the atomic oxygen generated from the oxidizing agent is oxidized by the ruthenium substrate as the substrate 20 to be processed. As a result, a process in which the oxidized portion is dissolved by the hydrofluoric acid in the treatment liquid 19 occurs. Thereby, the oxidation of the surface of the processing target substrate 20 and the dissolution of the oxidized portion in the treatment liquid 19 are promoted, reflecting the approximate shape of the surface of the transfer member, in other words, the surface of the transfer member can be considered. The shape is transferred.

<Other Modifications of First to Fourth Embodiments>

Incidentally, in the above-described respective embodiments, as shown in the second embodiment, the transfer device 10 is placed in close contact with the substrate 20 to be processed, and the processing liquid 19 is supplied. It is between the surface of the substrate 20 to be processed and the catalyst material 17, but the above embodiments are not limited to such a form.

For example, after the processing liquid 19 is supplied onto the surface of the substrate 20 to be processed, the transfer element 10 is placed in contact with or close to the substrate 20 to be processed. When such a sequence is employed, it is a preferable aspect that it is difficult to uniformly distribute the processing liquid 19 to the gap between the surface of the substrate 20 to be treated and the catalyst material 17.

Further, in each of the above-described embodiments, as shown in FIG. 2E, a supply device having the oxidation-treated substrate 20 and supplying the dissolved processing liquid 19 to the surface of the substrate 20 to be processed; and a transfer member Each of the processes is performed in the manufacturing apparatus 50 of the semiconductor device that contacts or approaches the arrangement device disposed on the surface of the substrate 20 to be processed. Further, the supply device and the arranging device further have a control unit for controlling each of the processes, for example, monitoring the concentration of the processing liquid 19 or the like.

<Fifth Embodiment>

In the present embodiment, the transfer element 10 of the first embodiment is replaced by a mesh-shaped transfer element (hereinafter referred to as a mesh-shaped transfer element) as shown in FIG. All of 10b are the same as those of the first embodiment. Therefore, the description overlapping with the first embodiment can be omitted.

The grid-shaped transfer element 10b of the present embodiment is made of "α mesh" (mesh number 400) manufactured by MESH Corporation, and has nickel (Ni) 4 μm, palladium (Pd) 1 μm, and platinum (Pt) 4 μm. The thickness of each layer is sequentially plated.

In the present embodiment, the processing target substrate 20 is immersed in the processing liquid 19, and the grid-shaped transfer element 10b is placed on the processing target substrate 20 for 30 minutes. Thereafter, the substrate to be processed 20 was washed with ultrapure water for 3 minutes.

As a result, the processing target substrate 20 on which the irregularities reflecting the shape of the mesh-shaped transfer element 10b are formed can be obtained. Fig. 10 is an optical microscopic photograph (planar photograph) of the surface of the substrate 20 to be processed in the present embodiment. In addition, Figure 11A shows the measurement pairs taken with a laser common rail focal microscope. A flat photo of the elephant department. Fig. 11B is a cross-sectional view showing the cross-sectional profile of the measurement target portion (X-X) in Fig. 11A.

As shown in Fig. 10, Fig. 11A, and Fig. 11B, although the respective unevenness has a slight difference, the surface of the concave structure is formed almost corresponding to the mesh portion of the mesh-shaped transfer element 10b. It is formed on the surface of the substrate 20 to be processed. Therefore, even in the present embodiment in which the transfer element having the fine mesh structure which is more easily supplied to the processing liquid 19 is used, it has been confirmed that the same effects as those of the above-described respective embodiments can be exhibited.

<Sixth embodiment>

In the present embodiment, the transfer element 10 used in the first embodiment is replaced with the mesh-shaped transfer element 10b, and the manufacturing device 50 of the semiconductor device according to the first embodiment is changed to a semiconductor device. The manufacturing apparatus 51 is the same as the first embodiment. Therefore, the description overlapping with the first and fifth embodiments can be omitted. In addition, the mesh-shaped transfer element 10b of the present embodiment is a base material which is very inexpensive compared with the "α mesh" (grid number 400) manufactured by MESH Corporation, and contains nickel (Ni). 15% of the palladium (Pd) alloy is about 0.5 to 1 μm, and platinum (Pt) is about 1 μm, which is formed by sequentially laminating the layers according to the thickness of each layer.

Fig. 12 is a schematic view showing a configuration of a main part of a manufacturing apparatus 51 of a semiconductor device according to the present embodiment. In addition, FIG. 12 is a view showing a state before the roller 57a is placed on the substrate 20 to be processed in the present embodiment. Fig. 13 is an explanatory view showing a state after the roller 57a is placed (during processing) with respect to the processing target substrate 20 in the present embodiment. Further, the processing target substrate 20 of the present embodiment is a single crystal germanium (100) substrate which is a semiconductor substrate.

As shown in Fig. 12, the manufacturing apparatus 51 of the semiconductor device of the present embodiment is roughly divided into a supply device 55 that supplies the processing liquid 19 to the surface of the processing target substrate 20, and a catalytic material (in the present embodiment). The grid-like transfer element 10b of the Pt (platinum) layer is placed in contact with or close to the arrangement device 59 disposed on the surface of the substrate 20 to be processed. More specifically, by the configuration device 59, in the present In the embodiment, the grid-shaped transfer element 10b is attached to the surface of the drum 57a having a circular cross-sectional shape perpendicular to the rotary shaft (RR in FIG. 12), thereby being disposed along the surface thereof. . In the state in which the processing liquid 19 is supplied to the surface of the processing target substrate 20, at least a part of the mesh-shaped transfer element 10b is brought into contact with or close to the arrangement state of the surface of the processing target substrate 20. And the roller 57a is moved. Then, as shown in FIG. 13, the arranging device 59 maintains its arrangement state, and has a control unit that relatively moves the drum 57a against the surface of the processing target substrate 20 and rotates it. In other words, after the position of the drum 57a as shown in FIG. 12 is opposite to the plane of the processing target substrate 20, the arranging device 59 causes the roller 57a to be applied to the surface of the processing target substrate 20 as shown in FIG. Move relative and rotate.

Therefore, in the present embodiment, after the processing liquid 19 at 60 ° C is supplied onto the surface of the substrate 20 to be processed, the different portions of the mesh-shaped transfer member 10b are continuously processed and processed by the rotation and movement of the roller 57a. The planes of the target substrates 20 are opposed to each other. Further, in the treatment liquid 19 of the present embodiment, the concentration of the hydrofluoric acid aqueous solution (HF) was 2.7 M, and the concentration of hydrogen peroxide water (H ₂ O ₂ ) was 8.1 M. Therefore, in the case of the present embodiment, in particular, when the concentration of hydrogen peroxide water (H ₂ O ₂ ) is 1 M or more and 10 M or less, platinum (Pt) selected from noble metals which are hard to be oxidized by the treatment liquid 19 of the present embodiment is used. At least one of a group consisting of palladium (Pd), rhodium (Rh), gold (Au), silver (Ag), and at least two or more of these alloys is preferably used as a catalyst.

Further, the material of the drum 57a in the present embodiment is nickel (Ni), and the diameter of the drum 57a is 35 mm. Further, the rotation speed of the drum 57a is about 0.27 rpm, and the moving speed is about 30 mm/sec. Therefore, for example, when a single crystal germanium wafer having a diameter of 6 inches is used as the substrate 20 to be processed, the processing of this embodiment can be completed in about 5 seconds. In the present embodiment, the entire processing target substrate 20 is processed by moving the roller 57a, and instead of the drum 57a being rotated only without moving, the structure and control state of the apparatus for moving the processing target substrate 20 are changed. Samples have also been adopted. again In addition, in order to increase the processing speed, for example, a well-known processing aspect including an integrated processing method in which a plurality of processing substrates 20 of a plurality of processing units are continuously processed is used.

As a result of the above-described processing, as shown in FIG. 13, after the roller 57a passes, the processing target substrate 20 having the uneven surface is formed. Fig. 14A is an optical micrograph (planar photograph) of the surface of the substrate 20 to be processed in the present embodiment. More specifically, when the present inventors observed and analyzed the surface of the substrate 20 to be processed in detail, the surface of the substrate 20 to be processed is different from the unevenness formed by the mesh-shaped transfer member 10b, in other words, In the vicinity of the mesh different from the position of the mesh in the grid-like transfer element 10b, more specifically, in the vicinity of the concave portion of the convex portion where the concave portion is not formed by the mesh, the formation is known. There are countless non-through holes. Further, in the case of the present embodiment, since the interval of the mesh is narrow, the convex portions are almost porous. Fig. 14B is an optical micrograph showing a cross section of the vicinity of the surface of the substrate 20 to be processed in the present embodiment. As shown in Fig. 14B, it is apparent that the thickness of the porous layer is as thin as 500 nm. In other words, the substrate to be processed 20 having a porous surface is formed by the manufacturing apparatus 51 of the semiconductor device of the present embodiment.

Here, when investigating the reflectance of the surface of the substrate 20 to be processed in the present embodiment, very interesting results were obtained. Fig. 15 is a graph showing the reflectance of the surface of the substrate 20 to be processed of the present embodiment which has been processed at 60 °C. In addition, for the purpose of comparison, the unprocessed processing target substrate 20 and the processing target substrate 20 having the surface of the embossed structure used in the transfer element 10 (corresponding to the convex-concave surface 12 of FIG. 1) are prepared. . In addition, in Fig. 15, the dotted line indicates the result of the unprocessed substrate 20 to be processed, and the single-dot chain line (described as "grain processing" in the figure) indicates the processing target of the surface having the above-described embossed structure. As a result of the substrate 20, the solid line indicates the result of the substrate 20 to be processed of the present embodiment. In addition, the measurement of the processing target substrate 20 of this embodiment was performed for the two samples in order to confirm the reproducibility.

As shown in Fig. 15, the reflectance of the light on the surface of the substrate 20 to be processed of the present embodiment is at least a reflectance measuring device (manufactured by JASCO Corporation, UV-visible near-infrared) The reflectance of light having a wavelength of 300 nm or more and 800 nm or less in the measurable range of the spectrophotometer, the type V-570) was confirmed to be remarkably small as compared with any of the comparative examples. In particular, the decrease in reflectance of the short-wavelength portion is more remarkable. According to the processing of the present embodiment, it is conceivable that the substrate 20 to be processed having the surface including the innumerable number of fine non-through holes is formed. Therefore, according to the manufacturing apparatus 51 of the semiconductor device of the present embodiment and the manufacturing method of the present invention, it is possible to clearly obtain the processing target substrate 20 in which the reflectance of light having a wavelength of 300 nm or more and 800 nm or less is suppressed to 15% or less. In particular, it has been found that the processing target substrate 20 which can greatly reduce the light reflectance is a manufacturing method and a manufacturing apparatus which are excellent in so-called industrial property and mass productivity in a state of only about 5 seconds. Further, as described above, even if there is a thin porous layer of about 500 nm, it is worth mentioning that the reflectance can be suppressed to 15% or less. This is because the porous layer is thin, and for example, it is possible to exhibit a peculiar effect of easily forming a pn junction. In general, in the formation of a porous tantalum layer using particles of platinum (Pt) or silver (Ag), the formation of a pn junction becomes difficult as the thickness of the porous layer becomes thicker. After the porous layer was dissolved using a sodium hydroxide (NaOH) aqueous solution, pn bonding was performed. In this case, in order to remove the porous layer, the reflectance will increase as a result. However, since the thickness of the porous layer of the present embodiment is extremely thin, it can be said that such a damage does not easily occur.

Furthermore, the inventors investigated the carrier lifetime of the surface of the substrate 20 to be processed of the present embodiment. Fig. 16 is a map showing the results of measurement of the lifetime of the substrate 20 to be processed in the present embodiment. Further, in Fig. 16, the processing of this embodiment is applied only to the area surrounded by the broken line.

As a result, as described above, even if the surface of the substrate 20 to be processed of the present embodiment is porous, the surface area is remarkably increased, and the reduction rate of the carrier lifetime is only 10% or less. As a result of this, in particular, when the surfaces of the embossed structure used in the above-described transfer substrate 10 are compared with each other, the difference is more remarkable. For example, for the embossed structure used in the transfer substrate 10 formed on the surface of the single crystal germanium (100), in order to expose the surface having a high interface energy density (111), the lifetime is relatively In the substrate 20 to be processed of the present embodiment, the reduction rate of the lifetime is suppressed to 10% or less.

<Modification (6) of the sixth embodiment>

The present embodiment is the same as the sixth embodiment except that the temperature and concentration of the treatment liquid 19 of the sixth embodiment are changed. Therefore, the description of the first, fifth, and sixth embodiments will be omitted. Here, with respect to the treatment liquid 19 of the present embodiment, the concentration of the hydrofluoric acid aqueous solution (HF) was 5.4 M, and the concentration of hydrogen peroxide water (H ₂ O ₂ ) was 7.2 M. Further, the temperature of the treatment liquid 19 of the present embodiment was 25 °C. In addition, the grid-shaped transfer element 10b of the present embodiment is a mesh-shaped transfer element of the fifth embodiment.

Under the above conditions, the same processing as in the sixth embodiment is performed with respect to the substrate to be processed 20. In addition, the manufacturing apparatus 51 of the semiconductor device of the present embodiment and the method of manufacturing the same are the same as the sixth embodiment. For example, when a single crystal germanium wafer having a diameter of 6 inches is used as the substrate 20 to be processed, it is possible to 5 seconds to complete the degree of processing, excellent industrial and even mass production.

Fig. 17 is an optical micrograph (planar photograph) of the surface of the substrate 20 to be processed in the present embodiment. As shown in Fig. 17, although the mesh structure was observed on the surface of the substrate 20 to be processed, it was confirmed that the shading in the optical microscope photograph was extremely inconspicuous, and the unevenness of the transfer by the mesh structure was confirmed. The depth is very shallow. This is considered to be because a part of the unevenness of the mesh structure reflected by the transfer is dissolved during the dissolution of the crucible.

In addition, FIG. 18 is a graph showing the reflectance of the surface of the substrate 20 to be processed in the present embodiment. In addition, for the purpose of comparison, the unprocessed processing target substrate 20 and the processing target substrate 20 having the surface of the embossed structure used in the transfer substrate 10 (corresponding to the convex-concave surface 12 of FIG. 1) are prepared. . In addition, the content described in the figure is the same as that of Fig. 15.

As shown in Fig. 18, in the measurement device similar to the sixth embodiment, the reflectance of light on the surface of the substrate 20 to be processed according to the present embodiment is light having a wavelength of 300 nm or more and 800 nm or less. The reflectance was confirmed to be significantly smaller as compared with any of the comparative examples. Further, even if compared with the results of the sixth embodiment, it is understood that the reflectance is remarkably lowered. Therefore, according to the manufacturing apparatus 51 of the semiconductor device of the present embodiment and the method of manufacturing the same, the substrate 20 to be processed having a reflectance of light of 300 nm or more and 800 nm or less is suppressed to 6% or less at room temperature (25 ° C). ) can be obtained under. In addition, the surface of the substrate 20 to be processed of the present embodiment has a porous layer having a thickness of about 500 nm from the surface as in the sixth embodiment. Therefore, in the present embodiment, even if there is a thin porous layer of about 500 nm, it is worth mentioning that the reflectance is suppressed to 6% or less.

<Modification (6) of the sixth embodiment>

This embodiment is the same as the sixth embodiment except that the crystal orientation of the processing target substrate 20 is changed. Therefore, the description overlapping with the first, fifth, and sixth embodiments can be omitted. Further, the processing target substrate 20 of the present embodiment is a single crystal germanium (111) substrate.

Fig. 19 is an optical micrograph (planar photograph) of the surface of the substrate 20 to be processed in the present embodiment. As shown in Fig. 19, even when the crystal orientation is different from that of the sixth embodiment, it has been confirmed that the same uneven shape can be formed. Here, it should be particularly noted that the manufacturing apparatus and the manufacturing method of the semiconductor device in the sixth embodiment do not depend on the crystal orientation of the semiconductor substrate. This is because the embossed structure used in the transfer substrate 10 described above can be applied to a single crystal germanium substrate having a plane orientation (100), the semiconductor device manufacturing apparatus 51 of the present embodiment, and a method of manufacturing the same The application does not depend on the face orientation. Further, it has been found that not only the single crystal germanium but also the case of applying the present embodiment to the polycrystalline germanium, the transfer and the porous surface of the mesh structure similar to the present embodiment can be formed.

<Modification (3) of the sixth embodiment>

The present embodiment is the same as the sixth embodiment except that the manufacturing apparatus 51 of the semiconductor device of the sixth embodiment is changed to the manufacturing apparatus 52 of the semiconductor device. Therefore, the description overlapping with the first and sixth embodiments can be omitted.

FIG. 20 is a schematic view showing a configuration of a main part of a manufacturing apparatus 52 of a semiconductor device according to the present embodiment. Further, in order to simplify the illustration, the mesh shape of the mesh-like transfer member 10b is not drawn. As shown in Fig. 20, the manufacturing apparatus 52 of the semiconductor device of the present embodiment is used in place of the supply device 55 of the sixth embodiment, and a part of the arrangement device 59 is used as a flow path of the processing liquid 19 on the side of the drum 57. Then, the supply device 56 that supplies the processing liquid 19 is used. Further, the drum 57b of the present embodiment is made of a sponge material. Therefore, while the roller 57b holds the state in which the processing liquid 19 supplied from the supply device 56 is immersed in the sponge material, the processing liquid 19 can be appropriately supplied to the outside, that is, the mesh-shaped transfer element 10b side. When the supply device 56 of the present embodiment is used, the same effects as those of the sixth embodiment can be exhibited. In addition, in the present embodiment, the supply of the processing liquid by the sponge-shaped roller 57b is changed by the supply amount of the processing liquid 19 supplied from the supply device 56, or the degree of lightness of the roller 57b to the processing target substrate 20, or the roller 57b. The rotation speed or the moving speed of the processing liquid 19 and the mesh-shaped transfer element 10b can be appropriately increased or decreased, which is a preferable aspect. As a specific example, the grid-shaped transfer element 10b of the present embodiment is pressed against the surface of the substrate 20 to be pressed for a few seconds, thereby exerting the effect of the sixth embodiment. The same effect. Therefore, in order to process the entire surface of the substrate 20 to be processed, it is only necessary to move the roller 57b relative to the surface of the substrate 20 to be processed and rotated while maintaining the contact state for a predetermined period of time.

Further, in the sixth embodiment and its modifications (1), (2), and (3), the shape of the drum 57a is circular in cross section perpendicular to the rotation axis (RR in Fig. 12). However, the shape of the drum is not limited to this. For example, as shown in Fig. 21A, even if the drum 57c having a fan-shaped cross-sectional shape perpendicular to the rotary shaft and the mesh-shaped transfer member 10b disposed on the outer peripheral curved surface thereof are used In other cases, the same effects as those of the embodiment can be exerted. In the case where the fan-shaped roller 57c is employed, there is an advantage that the angle range in which the drum 57c rotates is small. Further, instead of the drum 57a, a drum 57d having a polygonal cross section perpendicular to the rotary shaft (for example, an octagonal shape of the 21st B) may be employed. When the drum 57d is relatively rotated relative to the processing target substrate 20, in order to keep the distance from the processing target substrate 20 substantially constant, the cross-sectional shape perpendicular to the rotation axis of the drum 57d is preferably a positive polygonal shape. Further, the polygonal shape is not limited to an octagonal shape, and other types such as a hexagonal shape or a dodecagonal shape may be used. Further, as shown in Fig. 21C, it is also possible to adopt a mesh-shaped transfer element 10b which is provided only along the outer peripheral surface of a part of the drum 57d. Therefore, an appropriate roller and a mesh-shaped transfer element are selected in accordance with the object or area of the target substrate 20.

<Other Embodiments>

Incidentally, in the above-described respective embodiments, the substrate to be processed 20 is a single crystal germanium substrate or a polycrystalline germanium substrate, but is not limited thereto. For example, even a semiconductor substrate such as tantalum carbide (SiC), gallium arsenide (GaAs) or indium gallium arsenide (InGaAs) exhibits the same effects as those of the above embodiments. Further, the transfer element 10 is not limited to the n-type germanium substrate. For example, even a tantalum substrate other than the n-type, a tantalum carbide (SiC) substrate, a metal thin film substrate, a polymer resin, or a flexible substrate can exhibit the same effects as those of the above embodiments.

Further, in each of the above embodiments, platinum is used as the catalyst material 17, but the catalyst material 17 is not limited to platinum. For example, the catalyst medium 17 is selected from the group consisting of silver (Ag), palladium (Pd), gold (Au), rhodium (Rh), ruthenium (Ru), iridium (Ir), and an alloy containing at least one of them. At least one of the groups may be used as a decomposition catalyst for an oxidizing agent (for example, hydrogen peroxide) in the treatment liquid 19. For example, even if the catalyst material is an alloy containing palladium (Pd) and platinum (Pt) with gold (Au) as a main component, an alloy containing palladium (Pd) containing gold (Au) as a main component, and gold (Au) An alloy containing silver (Ag) and copper (Cu) as a main component, an alloy containing silver (Ag), copper (Cu) and palladium (Pd), and Mo (molybdenum) and gold (Au) as a main component W (tungsten) and Ir (铱) and platinum (Pt) Alloys, Fe (iron) and Co (cobalt), and alloys of Ni (nickel) and platinum (Pt) can exhibit at least some of the effects of the above embodiments. In addition, the addition of a small amount of other metals to each of the above-mentioned catalyst materials does not cause any hindrance. For example, in order to increase wear resistance, durability, and the like, a suitable and suitable metal may be added as long as it has a general knowledge in the technical field to which the present invention pertains.

Further, in the sixth embodiment and its modifications, an oxidizing agent having a particularly high concentration in the treatment liquid 19, that is, a noble metal which is not easily oxidized under the influence of hydrogen peroxide water (H ₂ O ₂ ), is selected, for example, At least one selected from the group consisting of platinum (Pt), palladium (Pd), rhodium (Rh), gold (Au), and alloys containing the same is used as a catalyst because it is easier to maintain its catalyst. Performance, so a better way. In addition, the meaning of "alloy" in this paragraph is also the same as the description of the above-mentioned catalyst material 17.

Further, the catalyst substance (i.e., the catalyst material 17) contributing to the promotion of oxidation is not limited to the above metal. For example, other known catalyst materials including an oxide compound, a carbon alloy compound, and an inorganic compound or various composites having functions equivalent to those described above can be used.

Further, in the first to third embodiments, the surface of the mother substrate (the n-type ruthenium substrate 11 in the first embodiment) and the catalyst member 17 of the transfer element 10 may be used as described above. In the first embodiment, in order to increase the adhesion, the anti-peeling layer or the water-repellent layer of the treatment liquid 19 exhibits a function of an intermediate layer interposed therebetween.

Further, in any of the above-described embodiments, in the aspect in which the transfer element has the catalyst material, the film or layer in which the catalyst material is formed on the surface of the transfer member is included, and in the transfer. The contact medium on the surface of the element is in a state of being adhered to a granular shape or an island shape, and includes a catalyst material on the transfer element as a catalyst, and a state in which the catalyst exhibits its function and performance. The metal which can be used as the above-mentioned respective catalyst materials 17 is typically a vapor deposition film formed by a known sputtering method, a plating method, a CVD method, or the like, or a coating film of a compound. A film formed by reduction or the like is formed, but the above embodiments are not limited to these films.

Further, in each of the above embodiments, a mixed aqueous solution of hydrofluoric acid (HF) and hydrogen peroxide water (H ₂ O ₂ ) is used as the treatment liquid 19, but the treatment liquid 19 is not limited to the mixed aqueous solution. For example, by using an aqueous solution selected from the group consisting of hydrogen peroxide water (H ₂ O ₂ ), potassium dichromate (K ₂ Cr ₂ O ₇ ), potassium permanganate (KMnO ₄ ), nitric acid (HNO ₃ ), sulfuric acid ( a mixed aqueous solution of at least one oxidizing agent and hydrofluoric acid (HF) in a group consisting of H ₂ SO ₄ ) and water in which oxygen (O ₂ ) or ozone (O ₃ ) is dissolved is used as the treatment liquid 19, and the above-described Effects of at least a part of each embodiment (for example, formation of a porous surface). Further, as an example of the treatment liquid 19, various kinds of highly oxidizing solutions or ozone water are used, and in particular, in the sixth embodiment and its modifications, precious metals which are not easily oxidized by the treatment liquid 19 are selected as the catalytic materials. Preferably.

Further, examples of the solar cell 100 in the fourth embodiment described above are also applicable to the first embodiment, the second embodiment, the fifth embodiment, the sixth embodiment, and other embodiments. In particular, in the sixth embodiment and the modified example, since the surface of the substrate 20 to be processed is porous, the surface area of the substrate 20 to be processed is remarkably increased, and the reflectance of light is remarkably low, so that solar cells can be obtained. The photoelectric conversion efficiency contributes to the increase in the short circuit current (J _SC ) value. Furthermore, it is particularly worth mentioning that even if the surface area is significantly increased, the lifetime of the carrier can be suppressed, and thus a high open circuit voltage (V _OC ) can be obtained.

Further, the base material of the mesh-shaped transfer element 10b used in the fifth embodiment, the sixth embodiment, and the modifications thereof is not limited. For example, even when the palladium (Pd) or platinum (Pt) is plated by plating nickel (Ni) on the organic polymer material to replace the mesh-shaped transfer element 10b, it has been confirmed that The same effects as those of the above embodiments are exerted. Therefore, it has been found that the treatment of each of the above embodiments can be carried out under conditions that are more excellent in mass productivity and industrial properties.

Further, as another aspect of the solar battery to which the sixth embodiment and its modifications are applied, the following configuration can be employed. First, the shape of a portion where the mesh of the mesh-shaped transfer element does not exist is formed in advance into the shape of a comb-shaped surface electrode of a general-purpose solar cell (typically in a plan view), and then Each process of the sixth embodiment and the like is performed. As a result, a convex portion corresponding to the comb-shaped surface electrode and a concave portion reflected by the shape of the mesh-shaped transfer element are formed on the surface of the tantalum substrate as the substrate to be processed. As a result, although the concave portion reflected by the shape of the mesh-shaped transfer element and the surface in the vicinity thereof are porous, the surface of the convex portion corresponding to the comb-shaped surface electrode does not become porous. Thereafter, a silver electrode was formed on the surface of the convex portion corresponding to the comb-shaped surface electrode by a known method to produce a solar cell. According to such a solar cell, for example, in the case where the substrate to be processed has a flat surface, the formation of the electrode can be facilitated by forming a silver electrode on the flat surface. On the other hand, in the field other than the electrode, the high open circuit voltage (V _OC ) can be simultaneously achieved due to the improvement of the short-circuit current (J _SC ) value and the effect of suppressing the decrease in the lifetime of the carrier.

In addition, in any of the above-described embodiments, the substrate to be processed 20 used for the solar cell is not only a polycrystalline germanium substrate of the fourth embodiment but also a single crystal germanium substrate or the amorphous germanium substrate. kind.

Further, in the fourth embodiment, the sixth embodiment, and the modifications thereof, the semiconductor device is exemplified by a solar cell, but the example of the semiconductor device is not limited to a solar cell. For example, in the device having the MEMS (Micro Electro Mechanical Systems) structure or the device having the large-scale integrated circuit (LSI), the formation processing of the uneven shape of the transfer elements 10, 10a, 10b of the above-described respective embodiments is used. Great contribution to the performance improvement of various devices. In addition, similarly, in the semiconductor device such as a light-emitting element or an optical device such as a light-receiving element, the formation of the uneven shape of the transfer elements 10, 10a, 10b of the above-described respective embodiments can greatly improve the performance of the device. Great contribution.

The disclosure of the above embodiments is merely illustrative of the embodiments and is not intended to limit the invention. Further, modifications that are within the scope of the invention, including other combinations of the embodiments, are also included in the scope of the claims.

<Industrial use possibility>

According to the present invention, it is possible to significantly contribute to improvement in performance and high performance of a semiconductor device manufactured using a substrate to be processed, which is produced by using a substrate for transfer. Therefore, it is widely used in the field of semiconductor devices typified by optical devices such as solar cells, light-emitting elements, and light-receiving elements.

11‧‧‧N-type 矽 substrate that has been treated with a mixed solution

Claims (12)

A method of manufacturing a semiconductor device, comprising: supplying a processing liquid that oxidizes and dissolves a semiconductor substrate to a supply process on a surface of the semiconductor substrate; and designing a transfer component having a catalyst medium a configuration process of contacting or approaching an arrangement state of the surface of the semiconductor substrate; and forming a concave-convex formation of the surface of the semiconductor substrate having a concave-convex surface or a porous shape by the supply engineering and the arrangement engineering Or a porous forming process; wherein, in the disposing project, a roller is included to maintain at least a portion of the transfer member disposed along a surface of the roller while contacting or approaching the semiconductor substrate The arrangement state of the surface causes the drum to relatively move and rotate relative to the surface of the semiconductor substrate. A method of manufacturing a semiconductor device, comprising: supplying a processing liquid that oxidizes and dissolves a semiconductor substrate to a supply process on a surface of the semiconductor substrate; and having a touch on or above the surface on which the unevenness is formed a transfer element of the medium material, which is disposed in contact with or close to an arrangement state of the surface of the semiconductor substrate; and the supply engineering and the arrangement process to form the uneven surface or the porous shape a concave-convex forming process or a porous forming process on the surface of the semiconductor substrate, Here, the transfer element is a tantalum substrate, and the catalyst medium is provided on the interlayer film formed on the surface of the transfer element. A method of manufacturing a semiconductor device, comprising: supplying a processing liquid that oxidizes and dissolves a semiconductor substrate to a supply process on a surface of the semiconductor substrate; and having a touch on or above the surface on which the unevenness is formed a transfer element of the medium material, which is disposed in contact with or close to an arrangement state of the surface of the semiconductor substrate; and the supply engineering and the arrangement process to form the uneven surface or the porous shape a concave-convex forming process or a porous forming process on the surface of the semiconductor substrate, wherein the contact medium is a film formed by a sputtering method, a plating method, or a chemical vapor deposition method, or a compound A film formed by reduction of a coating film. A method of manufacturing a semiconductor device, comprising: supplying a processing liquid that oxidizes and dissolves a semiconductor substrate to a supply process on a surface of the semiconductor substrate; and having a touch on or above the surface on which the unevenness is formed a transfer element of the medium material, which is disposed in contact with or close to an arrangement state of the surface of the semiconductor substrate; and the supply engineering and the arrangement process to form the uneven surface or the porous shape a concave-convex forming process or a porous forming process on the surface of the semiconductor substrate, Among them, the semiconductor device is a solar cell, an optical device, a device having a microelectromechanical system configuration, or a device having a large-scale integrated circuit. The method of manufacturing a semiconductor device according to claim 1, wherein the roller is used to supply the processing liquid. The method of manufacturing a semiconductor device according to claim 1, wherein the arrangement includes a roller for maintaining at least a portion of the transfer member disposed along a surface of the roller The roller is relatively moved and rotated with respect to the surface of the semiconductor substrate in a state of abutting against the surface of the semiconductor substrate. The method of manufacturing a semiconductor device according to claim 1, wherein the catalyst is a film formed by a sputtering method, a plating method, or a chemical vapor deposition method, or is coated with a compound. A film formed by reduction of a film. The method of manufacturing a semiconductor device according to claim 1, wherein the semiconductor device is a solar cell, an optical device, a device having a microelectromechanical system structure, or a device having a large-scale integrated circuit. A manufacturing apparatus for a semiconductor device, comprising: a supply device that supplies a processing liquid that oxidizes and dissolves a semiconductor substrate to a surface of the semiconductor substrate; and a transfer member having a catalyst material, a arranging device configured to contact or approach the surface of the semiconductor substrate, wherein the arranging device has a roller, and at least a portion of the transfer member disposed along a surface of the roller is associated with the semiconductor substrate While the surface is opposite, while maintaining contact or proximity to the semiconductor substrate The arrangement state of the surface of the board causes the drum to relatively move and rotate relative to the surface of the semiconductor substrate. The apparatus for manufacturing a semiconductor device according to claim 9, wherein the drum is used to supply the processing liquid. An element for transfer, which is an element having a catalyst, wherein the catalyst is disposed in contact with a oxidizing and dissolving treatment liquid on a surface of a semiconductor substrate. Or approaching the surface of the semiconductor substrate, whereby the surface of the semiconductor substrate is deformed in an uneven shape or a porous shape. The transfer member according to claim 11, wherein the transfer member is on a surface of a drum having a circular, polygonal or fan-shaped cross-sectional shape perpendicular to a rotary axis. And set.