JP3293766B2 - Semiconductor member manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for manufacturing a semiconductor member for forming a semiconductor device such as a semiconductor integrated circuit, a solar cell, a semiconductor laser, a light emitting diode, and the like.
In particular, the present invention relates to a method for manufacturing a semiconductor member including a step of transferring a semiconductor layer onto another substrate.

[0002]

2. Description of the Related Art A semiconductor member is known by the name of a semiconductor wafer, a semiconductor substrate, a semiconductor device, or the like, and includes a semiconductor element formed using a semiconductor region and a semiconductor element formed before the semiconductor element is formed. The state of the above shall be included.

Some of such semiconductor members have a semiconductor layer on an insulator.

The formation of a single-crystal Si semiconductor layer on an insulator involves
Widely known as silicon-on-insulator (SOI) technology, bulk Si for fabricating ordinary Si integrated circuits
Much research has been done because devices utilizing SOI technology have numerous advantages that cannot be achieved with substrates. That is, by using the SOI technology, 1. Dielectric separation is easy and high integration is possible. 2. Excellent radiation resistance. 3. Higher speed due to reduced stray capacitance. 4. Well step can be omitted; 5. Latch-up can be prevented. It is possible to obtain a fully-depleted field-effect transistor by thinning the film. These are described in detail in the following documents, for example. Special Issue: “Single-crystal silicon on no
n-single-crystal insulators "; edited by GWCullen,
Journal of Crystal Growth, volume 63, no 3, pp429〜59
0 (1983).

Further, in recent years, SOI has been
Many reports have been made as substrates for realizing high speed and low power consumption of OSFETs (IEEE SOI conference 19
94). In addition, when an SOI structure is used, since an insulating layer is provided below the device, the device isolation process can be simplified as compared with the case where the device is formed on a bulk Si wafer, and the device process steps are shortened. That is, it is expected that the total cost of the wafer cost and the process cost is reduced as compared with the MOSFET and the IC on the bulk Si together with the high performance.

Above all, a fully depleted MOSFET is expected to achieve higher speed and lower power consumption by improving the driving force.
The threshold voltage (Vth) of the MOSFET is generally determined by the impurity concentration of the channel portion. In the case of a fully depleted (FD) MOSFET using SOI, the thickness of the depletion layer is equal to the thickness of the SOI. It will be affected. Therefore, in order to produce a large-scale integrated circuit with high yield, uniformity of the SOI film thickness has been strongly desired.

[0007] Devices on compound semiconductors have high performance that cannot be obtained with Si, for example, high speed and light emission. At present, these devices are mostly GaAs
s and the like are formed by epitaxial growth on a compound semiconductor substrate. However, compound semiconductor substrates have problems such as being expensive, having low mechanical strength, and making it difficult to manufacture large-area wafers.

[0008] For these reasons, attempts have been made to heteroepitaxially grow compound semiconductors on Si wafers, which are inexpensive, have high mechanical strength, and can be used to produce large-area wafers.

Research on the formation of SOI substrates has been active since the 1970s. Initially, a method of heteroepitaxially growing single-crystal Si on a sapphire substrate, which is an insulator (SOS: Sapphire on Silicon), or a method using porous Si
Of SOI structure by dielectric isolation by oxidation of silicon (FIPOS: Fully Isolation by Porous Oxidized
Silicon), an oxygen ion implantation method has been well studied.

In the FIPOS method, an N-type Si layer is implanted with proton ions on the surface of a P-type Si single crystal substrate, (Imai et al., J. Cr.
ystal Growth, vol 63, 547 (1983)) or, after epitaxial growth and patterning, form islands, and anodize in HF solution so as to surround the Si islands from the surface to make only the P-type Si substrate porous. This is a method of separating an N-type Si island from a dielectric by accelerated oxidation. In this method, the separated Si region is determined before the device process, and there is a problem that the degree of freedom in device design may be limited.

The oxygen ion implantation method is a method called SIMOX first reported by K. Izumi. Si
After oxygen ions are implanted into the wafer at about 10 ¹⁷ to 10 ¹⁸ / cm ² , annealing is performed at a high temperature of about 1320 ° C. in an argon / oxygen atmosphere. As a result, oxygen ions implanted around the depth corresponding to the projection range (Rp) of the ion implantation are combined with Si to form an Si oxide layer. At this time, the Si layer which has been made amorphous by oxygen ion implantation on the upper part of the Si oxide layer is also recrystallized to become a single crystal Si layer. Defects contained in the Si layer on the surface were conventionally as high as 10 ⁵ / cm ² , but by reducing the amount of implanted oxygen to around 4 × 10 ¹⁷ / cm ² , it was possible to reduce it to 10 ² / cm ^2. Successful. However, the film quality of the Si oxide layer, the surface Si
Since the range of the implantation energy and the implantation amount for maintaining the crystallinity of the layer is narrow, the surface Si layer and the buried Si oxide
The thickness of the layer (BOX; Burried Oxide) was limited to a specific value. In order to obtain a surface Si layer having a desired thickness,
Sacrificial oxidation or epitaxial growth was required. In this case, there is a problem that the uniformity of the film thickness is deteriorated as a result of superimposing the deterioration due to these processes on the film thickness distribution.

Further, it has been reported that SIMOX has a formation defect region of Si oxide called a pipe.
One of the causes is considered to be foreign matter such as dust at the time of injection. In the portion where the pipe is present, device characteristics deteriorate due to leakage between the active layer and the supporting substrate.

As described above, the ion implantation of SIMOX has a larger implantation amount than the ion implantation used in a normal semiconductor process. Therefore, even if a dedicated apparatus is developed, the implantation time is long. Since the ion implantation is performed by raster-scanning or expanding the ion beam having a predetermined current amount, the implantation time is expected to increase with an increase in the area of the wafer. In addition, it has been pointed out that in the high-temperature heat treatment of a large-area wafer, problems such as generation of slip due to temperature distribution in the wafer become more severe. 1 for SIMOX
Since the heat treatment at a high temperature that is not normally used is required in the Si semiconductor process of 320 ° C., there is a concern that the importance of this problem will be further increased, including the development of the device.

In addition to the conventional SOI forming method as described above, in recent years, a Si single crystal substrate has been bonded to another thermally oxidized Si single crystal substrate using heat treatment or an adhesive to form an SOI structure. The method of forming has attracted attention. This method requires that the active layer for the device be uniformly thinned. That is, it is necessary to reduce the thickness of a Si single crystal substrate having a thickness of several hundred μm to the order of μm or less. There are three methods for reducing the thickness as follows. (1). Thinning by polishing (2). Thinning by local plasma etching (3). Thinning by Selective Etching It is difficult to achieve a uniform thinning by the polishing of (1).
In particular, when the thickness is reduced to sub-μm, the variation becomes several tens%, and the uniformity is a serious problem. Further, as the diameter of the wafer increases, the difficulty only increases.

In the method (2), the film thickness is reduced to about 1 to 3 μm by the method (1) in advance by the method (1), and then the film thickness distribution is measured at multiple points over the entire surface. Thereafter, based on this film thickness distribution, etching is performed while correcting the film thickness distribution by scanning a plasma using SF ₆ having a diameter of several mm or the like to reduce the film thickness to a desired film thickness. It is reported that this method can make the film thickness distribution approximately ± 10 nm. However, if foreign matter (particles) is present on the substrate during plasma etching, the foreign matter serves as an etching mask, so that a projection is formed on the substrate.

In addition, since the surface is rough immediately after the etching, touch polishing is required after the plasma etching. However, since the polishing amount is controlled by time management, the final film thickness control and the polishing are performed. It is pointed out that the film thickness distribution is deteriorated due to the above. Further, in the polishing, since an abrasive such as colloidal silica directly rubs the surface to be the active layer, there is a concern about formation of a crushed layer and introduction of processing distortion by polishing. Further, when the area of the wafer is increased, the plasma etching time increases in proportion to the increase of the wafer area, and there is a concern that the throughput may be significantly reduced.

The method (3) is a method in which a film structure that can be selectively etched is formed in advance on a substrate to be thinned. For example, boron is deposited on a P-type substrate at 10 ¹⁹ / cm
A thin layer of P ⁺ -Si and a thin layer of P-type Si, each having a concentration of ³ or more, are laminated by a method such as epitaxial growth to form a first substrate. After bonding this to the second substrate via an insulating layer such as an oxide film, the back surface of the first substrate is thinned in advance by grinding and polishing. Thereafter, the P ⁺ layer is exposed by selective etching of the P-type layer, and the P-type layer is exposed by selective etching of the P ⁺ layer, thereby completing the SOI structure. This method is detailed in Maszara's report (WPMaszara,
J. Electrochem. Soc., Vol. 138, 341 (1991)).

Although selective etching is considered to be effective for uniform thinning, the selectivity is not sufficient at most to 10 ² .

Touch polishing is required after etching because of poor surface properties after etching. However, as a result, as the film thickness decreases, the film thickness uniformity tends to deteriorate. In particular, in polishing, the polishing amount is controlled by time, but it is difficult to control the polishing amount because the polishing rate varies widely. Therefore, there is a particular problem in forming an ultra-thin SOI layer having a thickness of 100 nm.

The crystallinity of the SOI layer is poor due to the use of ion implantation, epitaxial growth on a high concentration B-doped Si layer or heteroepitaxial growth. Further, the surface properties of the surface to be bonded are inferior to those of a normal Si wafer. (C. Harendt, et.al., J. Elect. Mater. Vol.2
0,267 (1991), H. Baumgart, et.al., Extended Abstract of
ECS 1st International Symposium of Wafer Bonding,
pp-733 (1991), CEHunt, Extended Abstract of ECS 1s
t International Symposium of Wafer Bonding, pp-696
(1991)). Further, the selectivity of the selective etching largely depends on the concentration difference of impurities such as boron and the steepness of the profile in the depth direction. Therefore, when a high-temperature bonding anneal for increasing the bonding strength or a high-temperature epitaxial growth for improving the crystallinity are performed, the depth direction distribution of the impurity concentration is widened, and the etching selectivity is deteriorated. That is, it is difficult to achieve both the improvement in the selectivity of etching and the improvement in the bonding strength in the crystallinity.

Under these circumstances, the applicant of the present invention has previously described in
In Japanese Patent Publication No. 21338, a new method for manufacturing a semiconductor member was proposed. The method disclosed in this publication is as follows. That is, a member in which a non-porous single-crystal semiconductor region is arranged on a porous single-crystal semiconductor region is formed, and the surface of the member whose surface is made of an insulating material is formed on the surface of the non-porous single-crystal semiconductor region. After bonding, the porous single-crystal semiconductor region is removed by etching.

In addition, Yonehara et al., The inventor of the present invention, have reported a bonded SOI having excellent film thickness uniformity and crystallinity and capable of batch processing (T. Yonehara et.al., Appl. Phys. Let.
t.vol.64, 2108 (1994)). Hereinafter, this bonded SOI
Will be described with reference to FIGS. 4A to 4C.

In this method, the porous layer 32 on the Si substrate 31 is used as a material for performing selective etching. After epitaxially growing a non-porous single-crystal Si layer 33 on the porous layer 32, the second substrate 3 is
4 (FIG. 4A). The first substrate is thinned from the back surface by grinding or the like, and porous S
i is exposed (FIG. 4B). Exposed porous Si
Is removed by etching with a selective etching solution such as KOH, HF + H ₂ O ₂ (FIG. 4C). At this time,
Since the etching selectivity of porous Si to bulk Si (non-porous single-crystal Si) can be sufficiently increased to 100,000 times, the non-porous single-crystal Si previously grown on the porous
The layers can be transferred onto a second substrate with little decrease in film thickness to form an SOI substrate.
Therefore, the thickness uniformity of the SOI is substantially determined during the epitaxial growth. Since epitaxial growth can use a CVD apparatus usually used in a semiconductor process, according to a report by Sato et al. (SSDM95), the uniformity is realized within, for example, 100 nm ± 2%. In addition, the crystallinity of the epitaxial Si layer is good and is 3.5 × 1.
0 ² / cm ² was reported.

In the conventional method, the selectivity of etching depends on the difference in impurity concentration and the profile in the depth direction. Therefore, the temperature of heat treatment (bonding, epitaxial growth, oxidation, etc.) for expanding the concentration distribution is generally 800 ° C. or less. Was greatly restricted. On the other hand, in the etching in this method, since the difference in the structure between porous and bulk determines the etching speed, the restriction of the heat treatment temperature is small and
It is reported that heat treatment at about 180 ° C. is possible. For example, it is known that heat treatment after bonding increases the bonding strength between wafers and reduces the number and size of voids generated at the bonding interface. Further, in the etching based on such a structural difference, even if particles adhere to the porous Si, the uniformity of the film thickness is not affected.

However, a semiconductor substrate using bonding always requires two wafers, and almost one of them is wastefully removed and discarded by polishing, etching, etc., and the limited resources of the earth Is wasted. Therefore, in SOI by bonding, controllability and uniformity as well as cost reduction and improvement in economic efficiency are desired.

That is, there has been a demand for a method for producing an SOI substrate having sufficient quality with good reproducibility, and at the same time, realizing resource saving and cost reduction by reusing a wafer.

Under these circumstances, the present applicant has previously bonded two substrates, separated the bonded substrates in a porous layer, and removed residual porous material from one of the separated substrates. A method of manufacturing a semiconductor substrate by reusing this substrate has been proposed in Japanese Patent Application Laid-Open No. 7-302889.

One example of the method disclosed in the publication will be described below with reference to FIGS. 5 (a) to 5 (c).

After the surface layer of the first Si substrate 41 is made porous to form a porous layer 42, a single crystal Si layer 43 is formed thereon, and this single crystal Si layer and the first Si base are Is bonded to the main surface of another second Si substrate 44 via an insulating layer 45 (FIG. 5A). Thereafter, the wafer bonded with the porous layer is divided (FIG. 5B), and the SOI substrate is formed by selectively removing the porous Si layer exposed on the surface on the second Si substrate side. (FIG. 5C). The first substrate 41 can be reused by removing the remaining porous layer. And the division of the bonded wafer is
For example, it can be achieved by using the following method.

More specifically, a sufficient tensile force or pressure is applied evenly in a plane in the vertical direction. Wave energy such as ultrasonic waves is applied. Porous layer is exposed on the end face of the wafer to form porous Si. To some extent, insert something like a razor blade into it, ・ Expose a porous layer on the end face of the wafer, impregnate liquid such as water into porous Si, and then heat the whole bonded wafer Alternatively, the porous Si layer is broken by a method such as cooling and expanding the liquid, or applying a horizontal force to the second (or first) substrate with respect to the first (or second) substrate. Is used.

These are based on the fact that the mechanical strength of porous Si depends on porosity, but is considered to be sufficiently weaker than bulk Si. For example, if porosity is 5
If it is 0%, the mechanical strength can be considered to be half that of the bulk.
That is, when compressive, tensile or shearing force is applied to the bonded wafer, first, the porous Si layer is destroyed. Also, if the porosity is increased, the porous layer can be broken with a weaker force.

However, in practice, high quality epitaxial growth on porous Si is required, so that the porosity of the surface layer is reduced and the porosity of the inner side is increased for separation. It was hoped that something was done. For this reason, JP-A-07-3
As described in the example of Japanese Patent Publication No. 02889, the porosity is changed by controlling the current supplied during anodization.

The invention disclosed in Japanese Patent Application Laid-Open No. 07-302889 is an invention showing that a substrate once used in a semiconductor substrate manufacturing process can be reused in a semiconductor substrate manufacturing process. This is very useful in reducing costs. By the way, JP-A-07-
In the porousization of a silicon substrate disclosed in JP-A-302889, anodization is used. In order to make a large amount of silicon substrate porous without variation in a large-scale factory, anodization is performed by using silicon. Since the anodic reaction is used, it is necessary to use a silicon substrate having a strictly controlled specific resistance value. However, since a silicon substrate having a specified resistivity is relatively expensive, if a silicon substrate can be used without depending on the resistivity, the cost can be further reduced to manufacture an SOI substrate. Can be achieved.

An object of the present invention is to provide a method of manufacturing a semiconductor member having a step of bonding two substrates, and a method of manufacturing a semiconductor member capable of reusing a part of the substrate as a raw material of the semiconductor member. Is to do.

[0035]

Process for producing a semiconductor of the problem-solving means for the invention, P-type non than the silicon substrate to a silicon substrate
Forming a P-type impurity region having a high pure substance concentration,
Forming a first porous silicon layer in an object region;
A portion under the P-type impurity region where the porous silicon layer is formed
Forming a second porous silicon layer on the silicon substrate
And a non-porous semiconductor layer on the first porous silicon layer.
Forming a first substrate by forming
The non-porous semiconductor layer is positioned inside the body and the second substrate.
Bonding to obtain a multi-layer structure
In the second porous silicon layer.
A separating step of separating the multilayer structure.
And

[0036]

[0037]

In the method of manufacturing a semiconductor member according to the present invention, a diffusion region (high-concentration impurity region) in which an element capable of controlling conductivity is diffused is formed on at least one surface side of the silicon substrate. A porous silicon layer is formed in a region including. For this reason, the concentration of an element (impurity concentration in the semiconductor field) that can control conductivity in a diffusion region serving as a starting point of formation of a porous silicon layer can be set freely. Therefore, a relatively inexpensive silicon wafer or reclaimed wafer without resistance (reclaimed wafer is a monitor wafer during IC processing or a defective product) without using a silicon substrate with a specified resistivity. After the surface layer is removed by etching or polishing the wafer having the element on the surface, the surface is polished to a level that can be re-input to the IC process.). Therefore, according to the present invention, a high-quality semiconductor member can be manufactured at lower cost as compared with the conventional method.

Furthermore, the porous silicon layer region other than the diffusion region has a weaker structure than the diffusion region and the porous region, so that it is easily broken in the separation step and can be separated stably. That is, the fragile structure can be included in the porous silicon layer without changing the current used for forming the porous layer on the way.

That is, two porous Si layers can be automatically formed continuously without changing the anodizing conditions, and the surface porous S
The i layer can be effectively used for forming a high quality epitaxial layer, and the lower porous Si layer can be effectively used as a separation layer.

When the diffusion region is formed by the diffusion method, the diffusion region can be easily formed on both the main surface and the back surface of the silicon substrate. When the diffusion regions are formed on both surfaces of the silicon wafer as described above, the resistance between the back surface of the wafer and the + electrode during anodization for forming a porous layer can be reduced, and the current can flow within the wafer surface. There is a great effect to flow evenly. As a result, the porous Si layer is formed with a very uniform thickness. High concentration impurity regions (particularly P
Other methods for forming the ( ⁺ layer) include an ion implantation method and an epitaxial growth method. However, since these methods are single-sided processing unlike the diffusion method, a P ⁺ layer or the like cannot be simultaneously formed on the back surface. . In addition, despite the one-sided processing, it is disadvantageous in cost to the diffusion method. As described above, when the diffusion method is used, there is an advantage that both-side batch processing can be performed and the process cost is low.

According to the present invention, in obtaining a single-crystal semiconductor layer having excellent crystallinity on a second substrate which can be formed of an insulating substrate or the like, it is excellent in productivity, uniformity, controllability, and cost. A method for manufacturing a semiconductor member can be provided.

According to the present invention, even when a large-scale integrated circuit having an SOI structure is manufactured, an expensive SOS or SIM is required.
It is possible to provide a low-cost method for manufacturing a semiconductor member that can be substituted for OX.

[0044]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below. However, the present invention is not limited to these embodiments, and it is sufficient if the object of the present invention is achieved. .

[Formation of Diffusion Region] In the present invention, the elements capable of controlling the conductivity type to be diffused into a silicon substrate by a diffusion method are those generally used in semiconductor process technology. Refers to the element shown.

[0046]

[Table 1] As a diffusion method, it is preferable in terms of cost to employ a method capable of thermally diffusing an element capable of controlling the conductivity type into the silicon substrate. Examples of such a method include the diffusion methods shown in Table 2.

[0047]

[Table 2] In the present invention, a porous layer is formed in the diffusion region,
The formation of the porous layer is easier in the P-type diffusion region than in the N-type diffusion region. In view of this point, a list of B (boron) diffusion techniques is as shown in Table 3, for example.

[0048]

[Table 3] Also in the technique shown in Table 3, the element supplied from the source is basically diffused into the silicon substrate by the heat treatment in the "furnace".

For example, a diffusion method using a spin coat film
It can be performed as follows.

A mixture of B ₂ O ₃ and an organic binder and a solvent is uniformly applied on a silicon substrate (silicon wafer) using a spinner. This is dried and fired to form a B ₂ O ₃ film on the silicon substrate. Next, the silicon substrate is placed in a furnace as shown in FIG. 3 and heat treatment is performed to diffuse boron (B). In FIG. 3, 30
1 indicates a furnace, and 302 indicates a susceptor. Reference numeral 100 denotes a silicon substrate, and one surface of the substrate is coated with a B ₂ O ₃ film 150. For example, by performing a heat treatment at about 900 ° C. to 1300 ° C. using the apparatus shown in FIG.
Boron (B) can diffuse into the silicon substrate. In this case, a diffusion region is formed not only on the surface provided with B ₂ O ₃ but also on the back surface of this surface using a B ₂ O ₃ film formed on another adjacent silicon substrate as a source source. You.

When a diffusion layer is formed on both surfaces of a silicon substrate, HF is used when the porous layer is formed by anodization.
This is convenient because the contact resistance with the solution can be reduced.

The concentration of the element which can control the conductivity type contained in the diffusion region formed in the present invention is generally
5.0 × 10 ¹⁶ / cm ^{3 to} 5.0 × 10 ²⁰ / cm ³ , preferably 1.0 × 10 ¹⁷ / cm ^{3 to} 2.0 × 1
0 ²⁰ / cm ³ range, optimally 5.0 × 10 ¹⁷ / cm 3
The range of ^{3 to} 1.0 × 10 ²⁰ cm ³ is desirable in consideration of the porosity step and the characteristics of the epitaxial film formed on the porous silicon layer.

The thickness of the diffusion region formed in the present invention can be controlled by controlling the temperature and time of the heat treatment. The thickness of the diffusion layer is generally 100 ° to 100 μm.
m, preferably 500 ° -50 μm, optimally 5000
Å-30 μm. However, since the formation of the porosity, which is performed after the formation of the diffusion region, easily proceeds beyond the diffusion region, it is not always necessary to form the diffusion region thicker.

In the present invention, as the silicon substrate on which the diffusion layer is formed, in principle, any single crystal silicon substrate (silicon wafer) can be employed. However, for the purpose of manufacturing a semiconductor substrate at low cost, a relatively inexpensive silicon substrate with no resistance specified or an I
A monitor wafer used in the C process or a so-called reclaimed wafer whose surface is polished to a level that can be re-input to the IC process after removing the surface layer of the wafer having defective elements on the surface is used. It is desirable to do.

[Formation of Porous Silicon Layer] Porous Si
It was discovered by Uhlir et al. In the course of research on semiconductor electropolishing in 1956 (A. Uhlir, Bell Syst. Tech. J., vol.
35,333 (1956)). Porous Si can be formed by anodizing a Si substrate in an HF solution. Unagami et al. Studied the dissolution reaction of Si in anodization and reported that the anodic reaction of Si in HF solution requires holes, and the reaction is as follows (T. Unagami, J. Electrochem. Soc., Vol. 127, 476 (198
0)).

Si + 2HF + (2-n) e ⁺ → SiF ₂
+ 2H ⁺ + ne ^- SiF ₂ + 2HF → SiF ₄ + H ₂ SiF ₄ + 2HF → H ₂ SiF ₆ or Si + 4HF + (4-λ) e ⁺ → SiF ₄ + 4H ⁺ + λ
e ⁻ SiF ₄ + 2HF → H ₂ SiF ₆ Here, e ⁺ and e ⁻ represent holes and electrons, respectively. Further, n and λ are the number of holes required for dissolving the Si1 atom, and it is assumed that porous Si is formed when the condition of n> 2 or λ> 4 is satisfied.

From the above, it can be said that P-type Si having holes is made porous and N-type Si is not made porous. However, by changing the conditions, N-type Si can also be made porous.

In the present invention, porous Si having single crystallinity can be formed by anodizing a single crystal Si substrate in, for example, an HF solution. The porous layer has pores having a diameter of about 10 ^-1 to 10 nm.
^It has a structure like a sponge arranged at intervals of about ^{-1 to} 10 nm. Its density is 2.33 g of single crystal Si.
/ Cm ³ , by changing the HF solution concentration to 50 to 20% or changing the current density to 2.1 to 0.6.
g / cm ³ . That is, the porosity can be changed. In this way, the density of porous Si can be reduced to less than half that of single-crystal Si, but the single-crystal property is maintained, and a single-crystal Si layer can be epitaxially grown on top of the porous layer. It is.

The density of the porous layer is reduced to less than half since a large amount of voids are formed therein. As a result, the surface area is dramatically increased as compared with the volume, so that the chemical etching rate is significantly increased as compared with the ordinary etching rate of the single crystal layer.

The mechanical strength of porous Si depends on porosity, but is considered to be weaker than bulk Si. For example, if the porosity is 50%, the mechanical strength can be considered to be half that of the bulk. That is, compression on the bonded wafer,
When a tensile or shearing force is applied, the porous Si layer is first broken. Also, if the porosity is increased, the porous layer can be broken with a weaker force.

As described in the above-mentioned [Formation of Diffusion Region], the formation of the porosity can easily proceed beyond the diffusion region to a non-diffusion region. In the present invention, the thickness of the formed porous layer is generally 1 μm to 150 μm, preferably 2 μm to 80 μm, and optimally, considering the time required for forming the porous layer and the fragility of the porous layer. It is desirable to set it in the range of 5 μm to 50 μm.

[Non-Porous Semiconductor Layer] In the present invention, the non-porous semiconductor layer is preferably made of GaAs, InP, GaAs in addition to single crystal Si, polycrystal Si, amorphous Si.
P, GaAlAs, InAs, AlGaSb, InGa
Compound semiconductors such as As, ZnS, CdSe, CdTe, and SiGe can be used. The non-porous semiconductor layer may be one in which a semiconductor element such as an FET (Field Effect Transistor) has already been fabricated.

[First Substrate] The first substrate in which the non-porous semiconductor layer is disposed on the porous layer of the silicon substrate having the porous silicon layer is formed on the porous silicon layer formed in the silicon substrate. Forming the non-porous semiconductor layer described above,
Alternatively, it can be constituted by forming a porous silicon layer partially in a silicon substrate provided with a non-porous semiconductor layer.

In order to form a non-porous semiconductor layer on a porous silicon layer, low pressure CVD, plasma CVD, light CV
D, a CVD method such as MOCVD (Metal-Organic CVD), a sputtering method (including a bias sputtering method), a molecular beam epitaxial growth method, a liquid phase growth method, and the like can be employed.

[Second Substrate] The second substrate to which the non-porous semiconductor layer is transferred is, for example, a semiconductor substrate such as a single crystal silicon substrate, or an oxide film (a thermal oxide film is formed on the surface of the semiconductor substrate). And an insulating film such as a nitride film, a light-transmitting substrate such as a quartz substrate (Silica glass) or a glass substrate, a metal substrate, an insulating substrate such as alumina, and the like. Such a second base is appropriately selected according to the use of the semiconductor member.

[Bonding] In the present invention, the first base having the porous silicon layer and the non-porous semiconductor layer is bonded to the second base described above (the non-porous semiconductor layer). Is located inside) to obtain a multilayer structure. In the present invention, the multilayer structure in which the non-porous semiconductor layer is located on the inside refers to a structure in which the non-porous semiconductor layer constituting the first base is directly bonded to the second base, An insulating film such as an oxide film or a nitride film formed on the surface of the non-porous semiconductor layer, or a structure in which another film or the like is bonded to the second substrate is also included. That is, a structure in which the non-porous semiconductor layer is located inside the multilayer structure as compared to the porous silicon layer is called a multilayer structure in which the non-porous semiconductor layer is located inside.

Specifically, the first substrate and the second substrate are bonded together.
By making the bonding surface of the base material flat, the two substrates can be brought into close contact at room temperature, for example. In addition, anodic bonding, pressing, heat treatment, and the like can be performed to increase the bonding strength.

[Separation of Multilayered Structure] The porous silicon layer formed in the region other than the diffusion region is more fragile than the porous silicon layer formed in the diffusion region. Can be separated stably. As a specific separation method, a mechanical method of applying external pressure such as pressurization, pulling, shearing, a method of expanding the porous Si from the periphery by oxidation and applying an internal pressure in the porous Si, heating in a pulse shape,
There are methods such as applying thermal stress or softening,
It is not limited to these methods.

[Removal of Porous Layer] After the multilayer structure obtained by bonding the first substrate and the second substrate is separated at the porous Si layer, the porous S remaining on the separated substrate is separated.
i-layer, the mechanical strength of the porous layer Si layer is low,
By taking advantage of the very large surface area, it can be selectively removed. As a selective removal method, in addition to a mechanical method using grinding or polishing, a method such as chemical etching or ion etching (for example, reactive ion etching) using an etchant is employed. Can be.

When the porous Si layer is selectively etched using an etchant, the etchant is not limited to a mixed solution of 49% hydrofluoric acid and 30% hydrogen peroxide solution, but may be hydrofluoric acid or alcohol in hydrofluoric acid. A mixed solution obtained by adding an alcohol and a hydrogen peroxide solution to hydrofluoric acid, a mixed solution obtained by adding an alcohol to a buffered hydrofluoric acid, a buffered hydrofluoric acid,
Use a mixture of buffered hydrofluoric acid with aqueous hydrogen peroxide, a mixture of buffered hydrofluoric acid with alcohol and aqueous hydrogen peroxide, or a mixture of hydrofluoric acid, nitric acid, and acetic acid Can be.

After the porous layer is selectively removed, the semiconductor member obtained by transferring the non-porous semiconductor layer may be subjected to a heat treatment in an atmosphere containing hydrogen to increase the flatness of the non-porous semiconductor layer. it can.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.

[First Embodiment] A Si single crystal substrate 11 is prepared, and a P ⁺ layer 12 is formed on a main surface layer by a diffusion method (FIG. 1A). Thereafter, the main surface layer is made porous more deeply than the thickness of the P ⁺ layer 12, and a P ⁺ porous Si layer 13 and a lower porous Si layer 14 are formed (FIG. 1B). At least one non-porous thin film 15 is formed on the P ⁺ porous Si layer 13. Thereby, a first base is formed. The non-porous thin film 15 is made of single-crystal Si, polycrystalline Si, amorphous Si,
Alternatively, it is arbitrarily selected from a metal film, a compound semiconductor thin film, a superconducting thin film and the like. Further, the outermost surface layer is made of SiO ₂
May have the meaning that the bonding interface can be separated from the active layer. As shown in FIG. 1 (c), the second base 16 and the surface of the first base are brought into close contact with each other so that a multilayer structure in which the non-porous thin film 15 is located is obtained. Thereafter, the bonding may be strengthened by anodic bonding, pressing, heat treatment as necessary, or a combination thereof.

When single crystal Si is deposited, single crystal S
It is preferable to form the silicon oxide on the surface of i by a method such as thermal oxidation and then bond the silicon oxide. The second base can be selected from those described above. FIG. 1C shows a state in which the second substrate and the first substrate are bonded together with the insulating layer 17 interposed therebetween. When the non-porous thin film 15 is not Si, or when the second substrate is Si. If not, the insulating layer 17 may be omitted. At the time of bonding, it is also possible to sandwich three thin sheets with insulating thin plates.

Even when the non-porous thin film is formed of epitaxially grown single-crystal silicon, or when the non-porous thin film is formed of another material, heat treatment during epitaxial growth or heat treatment in subsequent steps is performed. In the case of using, the heat may cause rearrangement of the pores in the porous silicon layer to close the pores, thereby impairing the etching characteristics when the porous layer is removed by etching. Therefore, for example, a heat treatment is performed in advance at a temperature of about 200 ° C. to 700 ° C. to form a thin oxide film (while maintaining single crystallinity as a porous layer) on the side walls of the holes to prevent rearrangement, It is possible to stabilize the structure of the porous layer.

In order to form an epitaxial silicon film having extremely few defects, the following steps can be adopted.

Although the porous silicon layer maintains the structure as a single crystal, there is a possibility that a defect may enter the epitaxial silicon film due to a large number of holes existing on the surface of the porous silicon layer. Therefore, a method of closing the outermost surface of the porous silicon layer in contact with the epitaxial silicon film with single crystal silicon is conceivable.

One of the methods is a heat treatment in an atmosphere containing hydrogen. By this hydrogen heat treatment, migration of silicon atoms constituting the surface of the porous silicon occurs, and the outermost surface of the pores of the porous silicon layer is closed. The temperature of the heat treatment in this case is 500 ° C. to 130 ° C.
0 ° C., preferably in the range of 900 ° C. to 1300 ° C.

Apart from this method, a very small amount of a source gas containing silicon atoms is allowed to flow into the film forming chamber to form a silicon film at a very slow speed, and the outermost surface of the pores in the porous silicon layer is formed. Can be closed.

When a hole is closed and an epitaxial silicon film is formed after forming a thin oxide film on the side wall of the hole, when closing the hole, a single crystal is formed on the outermost surface of the porous silicon layer. It is desirable to be exposed. The single crystal can be exposed by exposing the outermost surface of the porous silicon layer having a thin oxide film formed on the side wall of the hole to an acid such as HF and removing the thin oxide film formed on the outermost surface.

Next, the substrate is separated by the porous Si layer 14 (FIG. 1D). The specific method of separation is as described above.

The separation layer is made of the lower porous Si layer 1 which is more fragile.
4, partially or entirely P ⁺ porous Si layer 1
3 may be used.

Next, the porous Si layers 13 and 14 are selectively removed. When the non-porous thin film is single-crystal Si, a normal Si etchant, a mixed solution of at least one of alcohol and hydrogen peroxide added to hydrofluoric acid, which is a selective etchant for porous Si, and hydrofluoric acid Electroless wet chemical etching of only the porous Si layers 13 and 14 using at least one of buffered hydrofluoric acid and a mixed solution of buffered hydrofluoric acid and at least one of alcohol and hydrogen peroxide solution Thus, the film previously formed on the porous material of the first substrate is left on the second substrate. As described in detail above, the large surface area of porous Si
It is possible to selectively etch only porous Si with the etchant i. Alternatively, the porous Si layers 13 and 14 are removed by selective polishing using the non-porous thin film layer 15 as a polishing stopper.

In the case where the compound semiconductor layer is formed on a porous material, only the porous Si layers 13 and 14 are chemically etched using an etching solution having a high Si etching rate with respect to the compound semiconductor to form a second layer. The thin-film single-crystal compound semiconductor layer 15 is left on the base 16 and formed. Alternatively, the porous Si layers 13 and 14 are removed by selective polishing using the single crystal compound semiconductor layer 15 as a polishing stopper.

FIG. 1E shows a semiconductor member obtained by the present invention. A non-porous thin film, for example, a single-crystal Si thin film 15 is flatly and uniformly thinned on the second substrate 16, and is formed over a large area over the entire wafer. If an insulating substrate is used as the second base 16, the semiconductor substrate thus obtained can be suitably used from the viewpoint of producing an insulated and separated electronic element.

After removing residual porous Si from the Si single crystal substrate 11, if the surface flatness is unacceptably rough, the surface is flattened, and then the Si single crystal forming the first base is again formed. It can be used as the substrate 11 or the next second base 16.

[Embodiment 2] In this embodiment, as shown in FIG. 2, P ⁺ layers 22 are formed on both surfaces of a Si single crystal substrate 21 constituting a first base by a diffusion method (FIG. 2A). )). Thereafter, the porous layer is made deeper than the thickness of the P ⁺ layer 22,
^{+ A} porous Si layer 23 and a lower porous Si layer 24 are formed (FIG. 2B). Next, a non-porous thin film 25 is formed on the P ⁺ porous Si layer 23, and second substrates 26 and 27 are bonded to each surface via an insulating layer 28 (FIG. 2).
(C)). Here, two sets of semiconductor members are to be manufactured at the same time. Each manufacturing process is the same as the process described in the first embodiment.

After removing residual porous Si from the Si single crystal substrate 21, if the surface flatness is unacceptably rough, the surface is flattened, and then the first Si single crystal substrate 21 or It can be used as the next second substrate 26 (or 27).

The materials and thicknesses of the support substrates 26 and 27 need not be the same. The non-porous thin film 25 does not need to have the same material, thickness, etc. on both sides.

[0090]

The present invention will be described below with reference to specific examples.

Example 1 A P ⁺ high-concentration layer of 5 μm was formed on a surface layer of a single-crystal Si substrate with no resistance specified by a diffusion method. At the same time, a P ⁺ high concentration layer was also formed on the back surface.

The specific formation of the P ⁺ high concentration layer was performed as follows. That is, the solution of B ₂ O ₃ in a solvent is S
It was applied to the main surface side of the i-substrate by using a spin coating method. Next, calcination was performed at a temperature of 140 ° C. to evaporate the solvent. The substrate thus obtained was placed in a diffusion furnace, and the inside of the furnace core tube was 1200
At a temperature of 6 ° C. for 6 hours, so-called drive-in diffusion was performed to form a P ⁺ high concentration layer.

After removing the applied film, the Si substrate on which the P ⁺ high-concentration layer was formed was immersed in an HF solution, anodized from the first surface side, and a porous layer was formed on the first surface side. Formed. The conditions of the anodization were as follows.

Current density: 7 (mA · cm ⁻² ) Anodizing solution: HF: H ₂ O: C ₂ H ₅ OH = 1: 1:
1 hour: 11 (min) Thickness of porous Si: 12 (μm) The thus obtained porous Si layer had a two-layer structure. The lower porous Si layer had a fine brittle structure compared to the surface layer.

This substrate was oxidized in an oxygen atmosphere at 400 ° C. for 1 hour. Due to this oxidation, the inner wall of the porous Si hole was covered with the thermal oxide film. Next, CVD (Chemic
al Vapor Deposition method)
μm epitaxial growth was performed. The growth conditions are as follows.

Source gas: SiH ₂ Cl ₂ / H ₂ gas flow rate: 0.5 / 180 l / min Gas pressure: 80 Torr Temperature: 950 ° C. Growth rate: 0.3 μm / min Further, the surface of this epitaxial Si layer is thermally oxidized. To form a 100 nm SiO ₂ layer.

[0097] Next, to obtain the said SiO ₂ layer surface, and the Si substrate (second substrate) of the surface formed an SiO ₂ layer of 500nm was separately prepared, the superimposed multilayer structures. When the 100 nm SiO ₂ layer and the epitaxial Si layer on the end face of the bonded wafer were separated by etching,
Porous Si edges appeared.

Next, when the bonded wafer was subjected to pyro-oxidation at 1000 ° C., the lower porous S
The two substrates were completely separated in the i-layer. When the peeled surface was observed, the porous Si on the outer peripheral portion of the wafer was changed to SiO ₂ , but the central portion was almost unchanged.

Then, the porous Si remaining on the second substrate side
The oxidized porous Si layer was selectively etched while being stirred with a mixed solution of 49% hydrofluoric acid and 30% hydrogen peroxide. The single-crystal Si remains without being etched, and the single-crystal Si
Was used as an etch stop material, the porous Si and the oxidized porous Si were selectively etched and completely removed.

The etching rate of the non-porous Si single crystal with respect to the etching solution is extremely low, the selectivity with respect to the etching rate of the porous layer reaches more than the tenth power, and the etching amount (number) About 10 angstroms)
Is a practically negligible decrease in film thickness.

Thus, a single-crystal Si layer having a thickness of 0.1 μm was formed on the Si oxide film. When the film thickness of the formed single crystal Si layer was measured at 100 points over the entire surface in the plane, the film thickness uniformity was 101 nm ± 3 nm.

Further, a heat treatment was performed in hydrogen at 1100 ° C. for 1 hour. When the surface roughness was evaluated with an atomic force microscope, the mean square roughness in a 50 μm square area was about 0.2.
nm, which was equivalent to that of a commercially available Si wafer.

As a result of observation of a cross section by a transmission electron microscope, S
No new crystal defects were introduced into the i-layer, and it was confirmed that good crystallinity was maintained.

Similar results were obtained without forming an oxide film on the surface of the epitaxial Si layer.

The porous Si remaining on the side of the first substrate and the oxidized porous Si are also subsequently treated with 49% hydrofluoric acid and 30% hydrofluoric acid.
Selective etching is carried out while stirring with a mixed solution with a hydrogen peroxide solution. The single-crystal Si remains without being etched, and the porous Si and the oxidized porous Si are selectively etched by using the single-crystal Si as a material for the etch stop, completely removed, and again as a first substrate having a high P concentration. It could be fed into the ⁺ layer diffusion step or the oxide film formation step as the second substrate.

(Example 2) Single-crystal Si substrate with no resistance specified
The surface layer of P was diffused in the same manner as in Example 1 by the diffusion method. ⁺Takano
A 5 μm thick layer was formed. P on the back⁺High concentration layer
Been formed. In the HF solution from the high concentration surface layer side,
Polarization was performed. The anodizing conditions were as follows.

Current density: 7 (mA · cm ⁻² ) Anodizing solution: HF: H ₂ O: C ₂ H ₅ OH = 1: 1:
1 hour: 11 (min) Thickness of porous Si: 12 (μm) The obtained porous Si layer had a two-layer structure. The lower porous Si layer had a fine brittle structure compared to the surface layer.

This substrate was oxidized in an oxygen atmosphere at 400 ° C. for 1 hour. Due to this oxidation, the inner wall of the porous Si hole was covered with the thermal oxide film. CVD (Chemical Vap) on porous Si
or Deposition) single-crystal Si was epitaxially grown to a thickness of 0.15 μm. The growth conditions are as follows.

Source gas: SiH ₂ Cl ₂ / H ₂ gas flow rate: 0.5 / 180 l / min Gas pressure: 80 Torr Temperature: 950 ° C. Growth rate: 0.3 μm / min Further, the surface of this epitaxial Si layer is thermally oxidized. To form a 100 nm SiO ₂ layer.

The surface of the SiO ₂ layer and 500 separately prepared
The surface and the surface of the Si substrate (second substrate) on which the SiO ₂ layer of nm was formed were brought into contact with each other.

After removing the back surface oxide film of the Si substrate,
The entire surface of the wafer was irradiated with a pulse of a CO ₂ laser having an output of about 500 to 1000 W from the substrate side. The CO ₂ laser is absorbed by the 500 nm SiO ₂ layer at the bonding interface, the temperature of the epitaxial layer and the porous Si layer in the vicinity rises sharply, and the thermal stress in the lower porous Si layer lowers the temperature. In a porous Si layer.

Thereafter, the porous Si remaining on the second substrate side is removed.
The layer was selectively etched with a mixture of 49% hydrofluoric acid and 30% hydrogen peroxide while stirring. The single-crystal Si remained without being etched, and the porous Si was selectively etched and completely removed using the single-crystal Si as a material for an etch stop.

Thus, a single-crystal Si layer having a thickness of 0.1 μm was formed on the Si oxide film. When the film thickness of the formed single crystal Si layer was measured at 100 points over the entire surface in the plane, the film thickness uniformity was 101 nm ± 3 nm.

Further, a heat treatment was performed in hydrogen at 1100 ° C. for 1 hour. When the surface roughness was evaluated with an atomic force microscope, the mean square roughness in a 50 μm square area was about 0.2.
nm, which was equivalent to that of a commercially available Si wafer.

As a result of observing the cross section with a transmission electron microscope,
No new crystal defects were introduced into the i-layer, and it was confirmed that good crystallinity was maintained.

Similar results were obtained without forming an oxide film on the surface of the epitaxial Si layer.

The porous Si remaining on the first substrate was also selectively etched while stirring with a mixed solution of 49% hydrofluoric acid and 30% hydrogen peroxide. Monocrystalline Si remained without being etched, the monocrystalline Si as an etch stopper, the porous Si was selectively etched is completely removed, a high concentration P ⁺ layer of the diffusion process as the first substrate again, Alternatively, it could be used as an oxide film forming step as a second substrate.

Example 3 A P ⁺ high-concentration layer of 5 μm was formed on a surface layer of a single-crystal Si substrate with no resistance specified by a diffusion method. At the same time, a P ⁺ high concentration layer was also formed on the back surface. The formation of the P ⁺ high concentration layer by the diffusion method was performed as follows.
That is, after setting the Si substrate in the furnace core tube, N ₂ gas is introduced into the liquid diffusion source containing BBr ₃ , bubbling is performed, and the vaporized gas is mixed with the carrier gas (N ₂ + O ₂ ) in the furnace core tube. Was introduced. After the B ₂ O ₃ layer was formed by maintaining the inside of the furnace core at a temperature of 1050 ° C. for 1 hour, the inside of the furnace core was then maintained at a temperature of 1200 ° C. for 6 hours, so-called drive-in diffusion was performed, and the P ⁺ high concentration was obtained. A layer was formed.

Next, anodization was performed in the HF solution from the high concentration surface layer side. The anodizing conditions were as follows.

Current density: 7 (mA · cm ⁻² ) Anodizing solution: HF: H ₂ O: C ₂ H ₅ OH = 1: 1:
1 hour: 11 (min) Porous Si thickness: 12 (μm) The porous Si layer had a two-layer structure. The lower porous Si layer had a fine brittle structure compared to the surface layer.

This substrate was oxidized in an oxygen atmosphere at 400 ° C. for 1 hour. Due to this oxidation, the inner wall of the porous Si hole was covered with the thermal oxide film. CVD (Chemical Vap) on porous Si
or Deposition) single-crystal Si was epitaxially grown by 0.15 μm. The growth conditions are as follows.

Source gas: SiH ₂ Cl ₂ / H ₂ gas flow rate: 0.5 / 180 l / min Gas pressure: 80 Torr Temperature: 950 ° C. Growth rate: 0.3 μm / min Further, the surface of this epitaxial Si layer is thermally oxidized. To form a 100 nm SiO ₂ layer.

The surface of the SiO ₂ layer was separately prepared from 500
The surface and the surface of the Si substrate (second substrate) on which the SiO ₂ layer of nm was formed were brought into contact with each other.

A pulse current of about 10 A to 100 A was applied only to the high-concentration P ⁺ layer of the first substrate, that is, the surface porous Si layer. The current is removed by removing SiO ₂ , exposing a high-concentration P ⁺ layer at the edge of the wafer, and flowing the wafer in such a manner that the + electrode and the − electrode that touch only the edge of the wafer sandwich the wafer. As a result, rapid thermal stress was applied to the lower porous Si layer, and separation occurred in the lower porous Si layer.

Thereafter, the porous Si remaining on the second substrate side is removed.
The layer is selectively etched with a mixture of 49% hydrofluoric acid and 30% hydrogen peroxide while stirring. The single-crystal Si remained without being etched, and the porous Si was selectively etched and completely removed using the single-crystal Si as a material for an etch stop.

Thus, a single-crystal Si layer having a thickness of 0.1 μm was formed on the Si oxide film. When the film thickness of the formed single crystal Si layer was measured at 100 points over the entire surface in the plane, the film thickness uniformity was 101 nm ± 3 nm.

Further, a heat treatment was performed in hydrogen at 1100 ° C. for 1 hour. When the surface roughness was evaluated with an atomic force microscope, the mean square roughness in a 50 μm square area was about 0.2.
nm, which was equivalent to that of a commercially available Si wafer.

As a result of observation of a cross section by a transmission electron microscope,
No new crystal defects were introduced into the i-layer, and it was confirmed that good crystallinity was maintained.

Similar results were obtained without forming an oxide film on the surface of the epitaxial Si layer.

At the same time, the porous Si remaining on the first substrate is also selectively etched while being stirred with a mixed solution of 49% hydrofluoric acid and 30% hydrogen peroxide. Monocrystalline Si remained without being etched, the monocrystalline Si as an etch stopper, the porous Si was selectively etched is completely removed, a high concentration P ⁺ layer of the diffusion process as the first substrate again, Alternatively, it could be used as an oxide film forming step as a second substrate.

Example 4 First Single Crystal S with No Resistance Specified
A P ⁺ high concentration layer of 5 μm was formed on the surface layer of the i-substrate by the same diffusion method as in Example 3. At the same time, a P ⁺ high concentration layer was also formed on the back surface. Anodization was performed in the HF solution from the high concentration surface layer side. The anodizing conditions were as follows.

Current density: 7 (mA · cm ⁻² ) Anodizing solution: HF: H ₂ O: C ₂ H ₅ OH = 1: 1:
1 hour: 11 (min) Porous Si thickness: 12 (μm) The porous Si layer had a two-layer structure. The lower porous Si layer had a fine brittle structure compared to the surface layer.

This substrate was oxidized in an oxygen atmosphere at 400 ° C. for 1 hour. Due to this oxidation, the inner wall of the porous Si hole was covered with the thermal oxide film. CVD (Chemical Vap) on porous Si
or Deposition) single-crystal Si was epitaxially grown by 0.15 μm. The growth conditions are as follows.

Source gas: SiH ₂ Cl ₂ / H ₂ gas flow rate: 0.5 / 180 l / min Gas pressure: 80 Torr Temperature: 950 ° C. Growth rate: 0.3 μm / min Further, the surface of this epitaxial Si layer is thermally oxidized. To form a 100 nm SiO ₂ layer.

The surface of the SiO ₂ layer was separately prepared from 500
The surface of the Si substrate (second substrate) on which the SiO ₂ layer of nm was formed was exposed to nitrogen plasma (in order to improve the bonding strength), and then superposed and contacted.
Annealed at 00 ° C for 10 hours.

When a sufficient tensile force was uniformly applied to the bonded wafers in a direction perpendicular to the plane and further in the plane, the wafers were separated in the fragile lower porous Si layer. Pressing or shearing force instead of tensile force also resulted in separation in the brittle lower porous Si layer. Further, even when a knife-like object was inserted into the gap between the edges of the bonded wafers like a wedge, the wafer was similarly separated in the fragile lower porous Si layer.

After that, the porous Si remaining on the second substrate side
The layer is selectively etched with a mixture of 49% hydrofluoric acid and 30% hydrogen peroxide while stirring. The single-crystal Si remained without being etched, and the porous Si was selectively etched and completely removed using the single-crystal Si as a material for an etch stop.

Thus, a single-crystal Si layer having a thickness of 0.1 μm was formed on the Si oxide film. When the film thickness of the formed single crystal Si layer was measured at 100 points over the entire surface in the plane, the film thickness uniformity was 101 nm ± 3 nm.

Further, a heat treatment was performed in hydrogen at 1100 ° C. for 1 hour. When the surface roughness was evaluated with an atomic force microscope, the mean square roughness in a 50 μm square area was about 0.2.
nm, which was equivalent to that of a commercially available Si wafer.

As a result of observation of a cross section by a transmission electron microscope,
No new crystal defects were introduced into the i-layer, and it was confirmed that good crystallinity was maintained.

Similar results were obtained without forming an oxide film on the surface of the epitaxial Si layer.

Further, the porous Si remaining on the first substrate side was also selectively etched while stirring with a mixed solution of 49% hydrofluoric acid and 30% hydrogen peroxide. Monocrystalline Si remained without being etched, the monocrystalline Si as an etch stopper, the porous Si was selectively etched is completely removed, a high concentration P ⁺ layer of the diffusion process as the first substrate again, Alternatively, it could be used as an oxide film forming step as a second substrate.

Example 5 A P ⁺ high-concentration layer having a thickness of 5 μm was formed on the surface layer of a single-crystal Si substrate with no resistance specified by the same diffusion method as in Example 1. At the same time, a P ⁺ high concentration layer was also formed on the back surface. Anodization was performed in the HF solution from the high concentration surface layer side. The anodizing conditions were as follows.

Current density: 7 (mA · cm ⁻² ) Anodizing solution: HF: H ₂ O: C ₂ H ₅ OH = 1: 1:
1 hour: 11 (min) Porous Si thickness: 12 (μm) The porous Si layer had a two-layer structure. The lower porous Si layer had a fine brittle structure compared to the surface layer.

The substrate was oxidized in an oxygen atmosphere at 400 ° C. for 1 hour. Due to this oxidation, the inner wall of the porous Si hole was covered with the thermal oxide film. CVD (Chemical Vap) on porous Si
or Deposition) single-crystal Si was epitaxially grown to a thickness of 0.15 μm. The growth conditions are as follows.

Source gas: SiH ₂ Cl ₂ / H ₂ gas flow rate: 0.5 / 180 l / min Gas pressure: 80 Torr Temperature: 950 ° C. Growth rate: 0.3 μm / min Further, the surface of this epitaxial Si layer is thermally oxidized. To form a 100 nm SiO ₂ layer.

The surface of the SiO ₂ layer and 500 separately prepared
The surface of the Si substrate (second substrate) on which the SiO ₂ layer having a thickness of nm was formed was exposed to nitrogen plasma, then superposed, brought into contact, and annealed at 400 ° C. for 10 hours.

When a sufficient tensile force was uniformly applied to the bonded wafers in a direction perpendicular to the plane and further in the plane, the wafers were separated in the fragile lower porous Si layer. Pressing or shearing force instead of tensile force also resulted in separation in the brittle lower porous Si layer. Further, even when a knife-like object was inserted into the gap between the edges of the bonded wafers like a wedge, the wafer was similarly separated in the fragile lower porous Si layer.

After that, the porous Si remaining on the second substrate side
The layer was selectively etched with an HF / HNO ₃ / CH ₃ COOH-based etchant. The porous Si was selectively etched and completely removed. The single-crystal Si was hardly etched and remained, and the porous Si was selectively etched using the single-crystal Si as a material for the etch stop and completely removed.

Thus, a single-crystal Si layer having a thickness of 0.1 μm was formed on the Si oxide film. When the film thickness of the formed single crystal Si layer was measured at 100 points over the entire surface in the plane, the film thickness uniformity was 101 nm ± 3 nm.

Further, a heat treatment was performed in hydrogen at 1100 ° C. for 1 hour. When the surface roughness was evaluated with an atomic force microscope, the mean square roughness in a 50 μm square area was about 0.2.
nm, which was equivalent to that of a commercially available Si wafer.

As a result of observation of a cross section by a transmission electron microscope, S
No new crystal defects were introduced into the i-layer, and it was confirmed that good crystallinity was maintained.

Similar results were obtained without forming an oxide film on the surface of the epitaxial Si layer.

At the same time, the porous Si remaining on the first substrate side is also selectively etched with an HF / HNO ₃ / CH ₃ COOH-based etchant. Monocrystalline Si remained without being etched, the monocrystalline Si as an etch stopper, the porous Si was selectively etched is completely removed, a high concentration P ⁺ layer of the diffusion process as the first substrate again,
Alternatively, it could be used as an oxide film forming step as a second substrate.

Example 6 A P ⁺ high-concentration layer of 5 μm was formed on the surface layer of a single-crystal Si substrate with no resistance specified by the same diffusion method as in Example 1. At the same time, a P ⁺ high concentration layer was also formed on the back surface. Anodization was performed in the HF solution from the high concentration surface layer side. The anodizing conditions were as follows.

Current density: 7 (mA · cm ⁻² ) Anodizing solution: HF: H ₂ O: C ₂ H ₅ OH = 1: 1:
1 hour: 11 (min) Thickness of porous Si: 12 (μm) The obtained porous Si layer had a two-layer structure. The lower porous Si layer had a fine brittle structure compared to the surface layer.

The substrate was oxidized in an oxygen atmosphere at 400 ° C. for 1 hour. Due to this oxidation, the inner wall of the porous Si hole was covered with the thermal oxide film. CVD (Chemical Vap) on porous Si
or Deposition) single-crystal Si was epitaxially grown by 0.15 μm. The growth conditions are as follows.

Source gas: SiH ₂ Cl ₂ / H ₂ gas flow rate: 0.5 / 180 l / min Gas pressure: 80 Torr Temperature: 950 ° C. Growth rate: 0.3 μm / min Further, the surface of this epitaxial Si layer is thermally oxidized. To form a 100 nm SiO ₂ layer.

The surface of the SiO ₂ layer and the surface of the separately prepared quartz substrate (second substrate) were respectively exposed to nitrogen plasma, then superposed, brought into contact, and annealed at 200 ° C. for 10 hours.

When a sufficient tensile force was uniformly applied to the bonded wafers in a direction perpendicular to the plane and further in the plane, the wafers were separated in the fragile lower porous Si layer. Pressing or shearing force instead of tensile force also resulted in separation in the brittle lower porous Si layer. Further, even when a knife-like object was inserted into the gap between the edges of the bonded wafers like a wedge, the wafer was similarly separated in the fragile lower porous Si layer.

Thereafter, the porous Si remaining on the second substrate side is removed.
The layer was selectively etched with a mixture of 49% hydrofluoric acid and 30% hydrogen peroxide while stirring. The single-crystal Si remained without being etched, and the porous Si was selectively etched and completely removed using the single-crystal Si as a material for an etch stop.

That is, a single-crystal Si layer having a thickness of 0.1 μm was formed on the quartz substrate. When the film thickness of the formed single crystal Si layer was measured at 100 points over the entire surface in the plane, the film thickness uniformity was 101 nm ± 3 nm.

Further, a heat treatment was performed in hydrogen at 970 ° C. for 2 hours. When the surface roughness was evaluated with an atomic force microscope,
Mean square roughness in the area of 50 μm square is about 0.2 nm
Was equivalent to a commercially available Si wafer.

As a result of observation of a cross section by a transmission electron microscope,
No new crystal defects were introduced into the i-layer, and it was confirmed that good crystallinity was maintained.

Similar results were obtained without forming an oxide film on the surface of the epitaxial Si layer.

The porous Si remaining on the first substrate was also selectively etched while stirring with a mixed solution of 49% hydrofluoric acid and 30% hydrogen peroxide. The single-crystal Si remains without being etched, and the porous Si is selectively etched and completely removed using the single-crystal Si as a material for an etch stop, and is again introduced into the step of diffusing a high-concentration P ⁺ layer as the first substrate. We were able to.

Example 7 A P ⁺ high-concentration layer having a thickness of 5 μm was formed on the surface layer of a single-crystal Si substrate with no resistance specified by the same diffusion method as in Example 3. At the same time, a P ⁺ high concentration layer was also formed on the back surface. Anodization was performed in the HF solution from the high concentration surface layer side. The anodizing conditions were as follows.

Current density: 7 (mA · cm ⁻² ) Anodizing solution: HF: H ₂ O: C ₂ H ₅ OH = 1: 1:
1 hour: 11 (min) Thickness of porous Si: 12 (μm) Thus, the porous Si layer had a two-layer structure. The lower porous Si layer had a fine brittle structure compared to the surface layer.

This substrate was oxidized in an oxygen atmosphere at 400 ° C. for 1 hour. Due to this oxidation, the inner wall of the porous Si hole was covered with the thermal oxide film. CVD (Chemical Vap) on porous Si
or Deposition) single crystal Si was epitaxially grown to 0.55 μm. The growth conditions are as follows.

Source gas: SiH ₂ Cl ₂ / H ₂ gas flow rate: 0.5 / 180 l / min Gas pressure: 80 Torr Temperature: 950 ° C. Growth rate: 0.3 μm / min Further, the surface of this epitaxial Si layer is thermally oxidized. To form a 100 nm SiO ₂ layer.

The surface of the SiO ₂ layer and a separately prepared 500 n
The surface of a Si substrate (second substrate) on which an m ₂ SiO ₂ layer was formed was brought into contact with the surface, and then a 100 nm SiO ₂ layer and an epitaxial S
When the i-layer was peeled off by etching, porous Si edges appeared.

When the bonded wafer was subjected to pyro-oxidation at 1000 ° C., the two substrates were completely separated in the lower porous Si layer in about 50 minutes. When the peeled surface was observed, the porous Si on the outer peripheral portion of the wafer was changed to SiO ₂ , but the central portion was almost unchanged.

Thereafter, the porous Si remaining on the second substrate side
The oxidized porous Si layer was selectively etched while being stirred with a mixed solution of 49% hydrofluoric acid and 30% hydrogen peroxide. The single-crystal Si remains without being etched, and the single-crystal Si
Was used as an etch stop material, the porous Si and the oxidized porous Si were selectively etched and completely removed.

The etching rate of the non-porous Si single crystal with respect to the etching solution is extremely low, the selectivity with respect to the etching rate of the porous layer reaches more than the tenth power, and the etching amount (number) About 10 angstroms)
Is a practically negligible decrease in film thickness.

That is, a single-crystal Si layer having a thickness of 0.5 μm was formed on the Si oxide film. When the thickness of the formed single-crystal Si layer was measured at 100 points over the entire surface, the uniformity of the thickness was 500 nm ± 15 nm.

Further, a heat treatment was performed in hydrogen at 1100 ° C. for 1 hour. When the surface roughness was evaluated with an atomic force microscope, the mean square roughness in a 50 μm square area was about 0.2.
nm, which was equivalent to that of a commercially available Si wafer.

As a result of observation of a cross section by a transmission electron microscope, S
No new crystal defects were introduced into the i-layer, and it was confirmed that good crystallinity was maintained.

Similar results were obtained without forming an oxide film on the surface of the epitaxial Si layer.

Further, the porous Si remaining on the first substrate side and the oxidized porous Si were also subsequently treated with 49% hydrofluoric acid and 30% hydrofluoric acid.
Selective etching was carried out while stirring with a mixed solution with a hydrogen peroxide solution. The single-crystal Si remains without being etched, and the porous Si and the oxidized porous Si are selectively etched by using the single-crystal Si as a material for the etch stop, completely removed, and again as a first substrate having a high P concentration. It could be fed into the ⁺ layer diffusion step or the oxide film formation step as the second substrate.

(Embodiment 8) A P ⁺ high concentration layer of 5 μm was formed on the surface layer of a single crystal Si substrate of a reclaimed wafer by the same diffusion method as in Embodiment 3. At the same time, a P ⁺ high concentration layer was also formed on the back surface. Anodization was performed in the HF solution from the high concentration surface layer side. The anodizing conditions were as follows.

Current density: 7 (mA · cm ⁻² ) Anodizing solution: HF: H ₂ O: C ₂ H ₅ OH = 1: 1:
1 hour: 11 (min) Thickness of porous Si: 12 (μm) The obtained porous Si layer had a two-layer structure. The lower porous Si layer had a fine brittle structure compared to the surface layer.

This substrate was oxidized in an oxygen atmosphere at 400 ° C. for 1 hour. Due to this oxidation, the inner wall of the porous Si hole was covered with the thermal oxide film. CVD (Chemical Vap) on porous Si
or Deposition) single-crystal Si was epitaxially grown by 0.15 μm. The growth conditions are as follows.

Source gas: SiH ₂ Cl ₂ / H ₂ gas flow rate: 0.5 / 180 l / min Gas pressure: 80 Torr Temperature: 950 ° C. Growth rate: 0.3 μm / min Further, the surface of this epitaxial Si layer is thermally oxidized. To form a 100 nm SiO ₂ layer.

The surface of the SiO ₂ layer and 500 separately prepared
The surface and the surface of the Si substrate (second substrate) on which the SiO ₂ layer of nm was formed were brought into contact with each other.

After removing the back surface oxide film of the first base, CO _{2 having} an output of about 500 to 1000 W was output from the first base.
The laser was irradiated on the entire surface of the wafer with a pulse. The CO ₂ laser is absorbed by the 500 nm SiO ₂ layer at the bonding interface, and the epitaxial layer and porous Si
The temperature of the layer rapidly increased, and separated in the lower porous Si layer due to the rapid thermal stress in the lower porous Si layer.

After that, the porous Si remaining on the second substrate side
The layer was selectively etched with a mixture of 49% hydrofluoric acid and 30% hydrogen peroxide while stirring. The single-crystal Si remained without being etched, and the porous Si was selectively etched and completely removed using the single-crystal Si as a material for an etch stop.

Thus, a single-crystal Si layer having a thickness of 0.1 μm was formed on the Si oxide film. When the film thickness of the formed single crystal Si layer was measured at 100 points over the entire surface in the plane, the film thickness uniformity was 101 nm ± 3 nm.

Further, a heat treatment was performed in hydrogen at 1100 ° C. for 1 hour. When the surface roughness was evaluated with an atomic force microscope, the mean square roughness in a 50 μm square area was about 0.2.
nm, which was equivalent to that of a commercially available Si wafer.

As a result of observation of a cross section by a transmission electron microscope, S
No new crystal defects were introduced into the i-layer, and it was confirmed that good crystallinity was maintained.

Similar results were obtained without forming an oxide film on the surface of the epitaxial Si layer.

Further, the porous Si remaining on the first substrate is also selectively etched while stirring with a mixed solution of 49% hydrofluoric acid and 30% hydrogen peroxide. Monocrystalline Si remained without being etched, the monocrystalline Si as an etch stopper, the porous Si was selectively etched is completely removed, a high concentration P ⁺ layer of the diffusion process as the first substrate again, Alternatively, it could be used as an oxide film forming step as a second substrate.

(Example 9) A P ⁺ high-concentration layer having a thickness of 5 µm was formed on the surface layer of a single-crystal Si substrate with no resistance specified by the same diffusion method as in Example 1. At the same time, a P ⁺ high concentration layer was also formed on the back surface. Anodization was performed in the HF solution from the high concentration surface layer side. The anodizing conditions were as follows.

Current density: 7 (mA · cm ⁻² ) Anodizing solution: HF: H ₂ O: C ₂ H ₅ OH = 1: 1:
1 hour: 11 (min) Thickness of porous Si: 12 (μm) The obtained porous Si layer had a two-layer structure. The lower porous Si layer had a fine brittle structure compared to the surface layer.

This substrate was oxidized at 400 ° C. for 1 hour in an oxygen atmosphere. Due to this oxidation, the inner wall of the porous Si hole was covered with the thermal oxide film. MOCVD (Metal Or
ganic Chemical Vapor Deposition)
As was epitaxially grown by 1 μm. The growth conditions are as follows.

Source gas: TMG / AsH ₃ / H ₂ gas pressure: 80 Torr temperature: 700 ° C. The surface of the GaAs layer and the surface of a separately prepared Si substrate (second base) were overlapped and brought into contact.

A pulse current of about 10 to 100 A was applied only to the high-concentration P ⁺ layer of the first substrate, that is, the surface porous Si layer. The current is removed by removing SiO ₂ , exposing a high-concentration P ⁺ layer at the edge of the wafer, and flowing the wafer in such a manner that the + electrode and the − electrode that touch only the edge of the wafer sandwich the wafer. as a result,
Sudden thermal stress was applied to the lower porous Si layer, and separation occurred in the lower porous Si layer.

Thereafter, the porous Si remaining on the second substrate side is removed.
Layer ethylenediamine + pyrocatechol + water (17m
(ratio of 1: 3g: 8ml) Etching was performed at 110 ° C.
The single-crystal GaAs remains without being etched, and the single-crystal Ga
Using As as an etch stop material, the porous Si and the oxidized porous Si were selectively etched and completely removed.

The etching rate of the non-porous GaAs single crystal with respect to the etching solution is extremely low, and the etching amount (about several tens angstroms) of the non-porous layer is a thickness reduction that can be practically ignored.

That is, a single-crystal GaAs layer having a thickness of 1 μm was formed on Si. Single crystal Ga formed
When the thickness of the As layer was measured at 100 points over the entire surface, the uniformity of the thickness was 1 μm ± 29.8 nm.

As a result of observation of a cross section by a transmission electron microscope, G
No new crystal defects were introduced in the aAs layer, and it was confirmed that good crystallinity was maintained.

By using a Si substrate with an oxide film as a supporting substrate, GaAs on an insulating film could be produced in a similar manner.

At the same time, the porous Si remaining on the first substrate is also selectively etched while being stirred with a mixed solution of 49% hydrofluoric acid and 30% hydrogen peroxide. Monocrystalline Si remained without being etched, the monocrystalline Si as an etch stopper, the porous Si was selectively etched is completely removed, a high concentration P ⁺ layer of the diffusion process as the first substrate again, Alternatively, it could be put into the bonding step as a second substrate.

Example 10 A high-concentration P ⁺ layer of 5 μm was formed on the surface layer of a single-crystal Si substrate with no resistance specified by the same diffusion method as in Example 1. At the same time, a P ⁺ high concentration layer was also formed on the back surface. Anodization was performed in the HF solution from the high concentration surface layer side. The anodizing conditions were as follows.

Current density: 7 (mA · cm ⁻² ) Anodizing solution: HF: H ₂ O: C ₂ H ₅ OH = 1: 1:
1 hour: 11 (min) Thickness of porous Si: 12 (μm) The obtained porous Si layer had a two-layer structure. The lower porous Si layer had a fine brittle structure compared to the surface layer.

This substrate was oxidized in an oxygen atmosphere at 400 ° C. for 1 hour. Due to this oxidation, the inner wall of the porous Si hole was covered with the thermal oxide film. MOCVD (Metal Or
ganic Chemical Vapor Deposition) method.
P was epitaxially grown by 1 μm.

The surface of the InP and the surface of the separately prepared quartz substrate (second substrate) were exposed to nitrogen plasma, respectively, overlapped, brought into contact, and annealed at 200 ° C. for 10 hours.

When a sufficient tensile force was applied to the bonded wafers evenly in the direction perpendicular to the plane and further in the plane, the wafers were separated in the fragile lower porous Si layer. Pressing or shearing force instead of tensile force also resulted in separation in the brittle lower porous Si layer. Further, even when a knife-like object was inserted into the gap between the edges of the bonded wafers like a wedge, the wafer was similarly separated in the fragile lower porous Si layer.

After that, the porous Si remaining on the second substrate side
The layer was selectively etched with a mixture of 49% hydrofluoric acid and 30% hydrogen peroxide while stirring. The single-crystal InP remained without being etched, and the porous Si was selectively etched and completely removed using the single-crystal InP as a material for an etch stop.

Thus, a single-crystal InP layer having a thickness of 1 μm was formed on the quartz substrate. Single crystal I formed
When the thickness of the nP layer was measured at 100 points over the entire surface, the uniformity of the thickness was 1 μm ± 29.0 nm.

As a result of observation of a cross section by a transmission electron microscope, I
No new crystal defects were introduced into the nP layer, and it was confirmed that good crystallinity was maintained.

At the same time, the porous Si remaining on the first substrate is also selectively etched while being stirred with a mixed solution of 49% hydrofluoric acid and 30% hydrogen peroxide. The single-crystal Si remains without being etched, and the porous Si is selectively etched and completely removed using the single-crystal Si as a material for an etch stop, and is again introduced into the step of diffusing a high-concentration P ⁺ layer as the first substrate. We were able to.

Example 11 A P ⁺ high-concentration layer of 5 μm was formed on both surface layers of a single-crystal Si substrate of a double-sided mirror with no resistance specified by the same diffusion method as in Example 1. Both-side anodization was performed in an HF solution. The anodizing conditions were as follows. The anodization was performed for 11 minutes on each side.

Current density: 7 (mA · cm ⁻² ) Anodizing solution: HF: H ₂ O: C ₂ H ₅ OH = 1: 1:
1 hour: 11 × 2 (min) Thickness of porous Si: 12 (μm) Each porous Si layer had a two-layer structure. The lower porous Si layer had a fine brittle structure compared to the surface layer.

This substrate was oxidized in an oxygen atmosphere at 400 ° C. for 1 hour. Due to this oxidation, the inner wall of the porous Si hole was covered with the thermal oxide film. CVD (Chemical
0.15 μm of single crystal Si by Vapor Deposition method
It was epitaxially grown. The growth conditions are as follows.

Source gas: SiH ₂ Cl ₂ / H ₂ gas flow rate: 0.5 / 180 l / min Gas pressure: 80 Torr Temperature: 950 ° C. Growth rate: 0.3 μm / min A 100 nm SiO ₂ layer was formed by oxidation.

The surface of the SiO ₂ layer and 500 separately prepared
The surfaces of two Si substrates (second substrates) on which an SiO ₂ layer having a thickness of 10 nm are formed are overlapped and brought into contact with each other, and then the 100 nm SiO ₂ layer and the epitaxial Si layer on the end surface of the bonded wafer are peeled off by etching. As a result, porous Si edges appeared.

When the bonded wafer was subjected to pyro-oxidation at 1000 ° C., the two substrates were completely separated in the lower porous Si layer in about 50 minutes. However, it is preferable to perform oxidation for several hours because there is variation between wafers. When the peeled surface was observed, the porous Si on the outer peripheral portion of the wafer was changed to SiO ₂ , but the central portion was almost unchanged.

Thereafter, the porous Si layer and the oxidized porous Si layer remaining on the side of the two second substrates were washed with 49% hydrofluoric acid and 3%.
Selective etching was performed while stirring with a mixed solution of 0% hydrogen peroxide solution. The single-crystal Si remained without being etched, and the porous Si and the oxidized porous Si were selectively etched using the single-crystal Si as a material for an etch stop and completely removed.

That is, two single-crystal Si layers having a thickness of 0.1 μm were formed on the Si oxide film. When the film thickness of the formed single crystal Si layer was measured at 100 points over the entire surface in the plane, the film thickness uniformity was 101 nm ± 3 nm.

Further, a heat treatment was performed in hydrogen at 1100 ° C. for 1 hour. When the surface roughness was evaluated with an atomic force microscope, the mean square roughness in a 50 μm square area was about 0.2.
nm, which was equivalent to that of a commercially available Si wafer.

As a result of observation of a cross section by a transmission electron microscope,
No new crystal defects were introduced into the i-layer, and it was confirmed that good crystallinity was maintained.

The same result was obtained without forming an oxide film on the surface of the epitaxial Si layer.

Further, the porous Si remaining on the first substrate side and the oxidized porous Si are also subsequently treated with 49% hydrofluoric acid and 30% hydrofluoric acid.
Selective etching was carried out while stirring with a mixed solution with a hydrogen peroxide solution. The single-crystal Si remains without being etched, and the porous Si and the oxidized porous Si are selectively etched by using the single-crystal Si as a material for the etch stop, completely removed, and again as a first substrate having a high P concentration. It could be fed into the ⁺ layer diffusion step or the oxide film formation step as the second substrate.

Example 12 A P ⁺ high-concentration layer was formed to a thickness of 10 μm on the surface layer of a single-crystal Si substrate with no resistance specified in the same manner as in Example 1 except that drive-in diffusion was performed for 10 hours.
At the same time, a P ⁺ high concentration layer was also formed on the back surface. Anodization was performed in the HF solution from the high concentration surface layer side. The anodizing conditions were as follows.

Current density: 7 (mA · cm ⁻² ) Anodizing solution: HF: H ₂ O: C ₂ H ₅ OH = 1: 1:
1 hour: 15 (min) Thickness of porous Si: 16 (μm) The obtained porous Si layer had a two-layer structure. The lower porous Si layer had a fine brittle structure compared to the surface layer.

This substrate was oxidized in an oxygen atmosphere at 400 ° C. for 1 hour. Due to this oxidation, the inner wall of the porous Si hole was covered with the thermal oxide film. CVD (Chemical Vap) on porous Si
or Deposition) single-crystal Si was epitaxially grown by 0.15 μm. The growth conditions are as follows.

Source gas: SiH ₂ Cl ₂ / H ₂ gas flow rate: 0.5 / 180 l / min Gas pressure: 80 Torr Temperature: 950 ° C. Growth rate: 0.3 μm / min Further, the surface of this epitaxial Si layer is thermally oxidized. To form a 100 nm SiO ₂ layer.

The surface of the SiO ₂ layer and 500 separately prepared
The surface and the surface of the Si substrate (second substrate) on which the SiO ₂ layer of nm was formed were brought into contact with each other. Thereafter, heat treatment was performed at 1180 ° C. for 5 minutes to increase the bonding strength.

When a sufficient tensile force was applied to the bonded wafers evenly in the direction perpendicular to the plane and further in the plane, the wafers were separated in the fragile lower porous Si layer. Pressing or shearing force instead of tensile force also resulted in separation in the brittle lower porous Si layer. Further, even when a knife-like object was inserted into the gap between the edges of the bonded wafers like a wedge, the wafer was similarly separated in the fragile lower porous Si layer.

Thereafter, the porous Si remaining on the second substrate side
The layer was selectively etched with a mixture of 49% hydrofluoric acid and 30% hydrogen peroxide while stirring. The single-crystal Si remained without being etched, and the porous Si was selectively etched and completely removed using the single-crystal Si as a material for an etch stop.

That is, a single-crystal Si layer having a thickness of 0.1 μm was formed on the Si oxide film. When the film thickness of the formed single crystal Si layer was measured at 100 points over the entire surface in the plane, the film thickness uniformity was 101 nm ± 3 nm.

Further, heat treatment was performed in hydrogen at 1100 ° C. for 1 hour. When the surface roughness was evaluated with an atomic force microscope, the mean square roughness in a 50 μm square area was about 0.2.
nm, which was equivalent to that of a commercially available Si wafer.

As a result of observation of a cross section by a transmission electron microscope, S
No new crystal defects were introduced into the i-layer, and it was confirmed that good crystallinity was maintained.

The same result was obtained without forming an oxide film on the surface of the epitaxial Si layer.

At the same time, the porous Si remaining on the first substrate was also selectively etched while stirring with a mixed solution of 49% hydrofluoric acid and 30% hydrogen peroxide. Monocrystalline Si remained without being etched, the monocrystalline Si as an etch stopper, the porous Si was selectively etched is completely removed, a high concentration P ⁺ layer of the diffusion process as the first substrate again, Alternatively, it could be used as an oxide film forming step as a second substrate.

Example 13 A P ⁺ high-concentration layer of 10 μm was formed on the surface layer of a single-crystal Si substrate with no resistance specified in the same manner as in Example 3 except that the drive-in diffusion was performed for 10 hours.
At the same time, a P ⁺ high concentration layer was also formed on the back surface. Anodization was performed in the HF solution from the high concentration surface layer side. The anodizing conditions were as follows.

Current density: 7 (mA · cm ⁻² ) Anodizing solution: HF: H ₂ O: C ₂ H ₅ OH = 1: 1:
1 hour: 15 (min) Thickness of porous Si: 16 (μm) The obtained porous Si layer had a two-layer structure. The lower porous Si layer had a fine brittle structure compared to the surface layer.

This substrate was oxidized in an oxygen atmosphere at 400 ° C. for 1 hour. Due to this oxidation, the inner wall of the porous Si hole was covered with the thermal oxide film. CVD (Chemical Vap) on porous Si
or Deposition) single-crystal Si was epitaxially grown by 0.15 μm. The growth conditions are as follows.

Source gas: SiH ₂ Cl ₂ / H ₂ gas flow rate: 0.5 / 180 l / min Gas pressure: 80 Torr Temperature: 950 ° C. Growth rate: 0.3 μm / min Further, the surface of this epitaxial Si layer is thermally oxidized. To form a 100 nm SiO ₂ layer.

The surface of the SiO ₂ layer was superimposed on and brought into contact with the surface of a separately prepared Si substrate (second substrate). Then, at 1180 ° C to increase the bonding strength
Heat treatment was performed for 5 minutes.

When a sufficient tensile force was applied to the bonded wafers evenly in the direction perpendicular to the plane and further in the plane, the wafers were separated in the fragile lower porous Si layer. Pressing or shearing force instead of tensile force also resulted in separation in the brittle lower porous Si layer. Further, even when a knife-like object was inserted into the gap between the edges of the bonded wafers like a wedge, the wafer was similarly separated in the fragile lower porous Si layer.

Thereafter, the porous Si remaining on the second substrate side
The layer was selectively etched with a mixture of 49% hydrofluoric acid and 30% hydrogen peroxide while stirring. The single-crystal Si remained without being etched, and the porous Si was selectively etched and completely removed using the single-crystal Si as a material for an etch stop.

Thus, a single-crystal Si layer having a thickness of 0.1 μm was formed on the Si oxide film. When the film thickness of the formed single crystal Si layer was measured at 100 points over the entire surface in the plane, the film thickness uniformity was 101 nm ± 3 nm.

Further, a heat treatment was performed in hydrogen at 1100 ° C. for 1 hour. When the surface roughness was evaluated with an atomic force microscope, the mean square roughness in a 50 μm square area was about 0.2.
nm, which was equivalent to that of a commercially available Si wafer.

As a result of observation of a cross section by a transmission electron microscope,
No new crystal defects were introduced into the i-layer, and it was confirmed that good crystallinity was maintained.

The porous Si remaining on the first substrate was also selectively etched while stirring with a mixed solution of 49% hydrofluoric acid and 30% hydrogen peroxide. Monocrystalline Si remained without being etched, the monocrystalline Si as an etch stopper, the porous Si was selectively etched is completely removed, a high concentration P ⁺ layer of the diffusion process as the first substrate again, Alternatively, it could be put into the bonding step as a second substrate.

(Example 14) A P ⁺ high-concentration layer of 5 µm was formed on the surface layer of a single-crystal Si substrate of a reclaimed wafer by a diffusion method. At the same time, a P ⁺ high concentration layer was also formed on the back surface. Anodization was performed in the HF solution from the high concentration surface layer side. The anodizing conditions were as follows.

Current density: 7 (mA · cm ⁻² ) Anodizing solution: HF: H ₂ O: C ₂ H ₅ OH = 1: 1:
1 hour: 15 (min) Thickness of porous Si: 16 (μm) The obtained porous Si layer had a two-layer structure. The lower porous Si layer had a fine brittle structure compared to the surface layer.

This substrate was oxidized in an oxygen atmosphere at 400 ° C. for 1 hour. Due to this oxidation, the inner wall of the porous Si hole was covered with the thermal oxide film. CVD (Chemical Vap) on porous Si
or Deposition) single-crystal Si was epitaxially grown by 0.15 μm. The growth conditions are as follows.

Source gas: SiH ₂ Cl ₂ / H ₂ gas flow rate: 0.5 / 180 l / min Gas pressure: 80 Torr Temperature: 950 ° C. Growth rate: 0.3 μm / min Further, the surface of this epitaxial Si layer is thermally oxidized. To form a 100 nm SiO ₂ layer.

The surface of the SiO ₂ layer and 500 separately prepared
The surface of the Si substrate (second substrate) on which the SiO ₂ layer having a thickness of nm was formed was exposed to nitrogen plasma, then superposed, brought into contact, and annealed at 400 ° C. for 10 hours.

When a sufficient tensile force was applied to the bonded wafers evenly in the direction perpendicular to the plane and further in the plane, the wafers were separated in the fragile lower porous Si layer. Pressing or shearing force instead of tensile force also resulted in separation in the brittle lower porous Si layer. Further, even when a knife-like object was inserted into the gap between the edges of the bonded wafers like a wedge, the wafer was similarly separated in the fragile lower porous Si layer.

Thereafter, the porous Si remaining on the second substrate side
The layer was selectively etched with a mixture of 49% hydrofluoric acid and 30% hydrogen peroxide while stirring. The single-crystal Si remained without being etched, and the porous Si was selectively etched and completely removed using the single-crystal Si as a material for an etch stop.

That is, a single-crystal Si layer having a thickness of 0.1 μm was formed on the Si oxide film. When the film thickness of the formed single crystal Si layer was measured at 100 points over the entire surface in the plane, the film thickness uniformity was 101 nm ± 3 nm.

Further, a heat treatment was performed in hydrogen at 1100 ° C. for 1 hour. When the surface roughness was evaluated with an atomic force microscope, the mean square roughness in a 50 μm square area was about 0.2.
nm, which was equivalent to that of a commercially available Si wafer.

As a result of observation of a cross section by a transmission electron microscope, S
No new crystal defects were introduced into the i-layer, and it was confirmed that good crystallinity was maintained.

A similar result was obtained without forming an oxide film on the surface of the epitaxial Si layer.

The porous Si remaining on the first substrate was also selectively etched while stirring with a mixed solution of 49% hydrofluoric acid and 30% hydrogen peroxide. Monocrystalline Si remained without being etched, the monocrystalline Si as an etch stopper, the porous Si was selectively etched is completely removed, a high concentration P ⁺ layer of the diffusion process as the first substrate again, Alternatively, it could be used as an oxide film forming step as a second substrate.

(Example 15) A P ⁺ high concentration layer of 5 µm was formed on the surface layer of a single crystal Si substrate of a reclaimed wafer by the same diffusion method as in Example 1. At the same time, a P ⁺ high concentration layer was also formed on the back surface. Anodization was performed in the HF solution from the high concentration surface layer side. The anodizing conditions were as follows.

Current density: 7 (mA · cm ⁻² ) Anodizing solution: HF: H ₂ O: C ₂ H ₅ OH = 1: 1:
1 hour: 15 (min) Thickness of porous Si: 16 (μm) The obtained porous Si layer had a two-layer structure. The lower porous Si layer had a fine brittle structure compared to the surface layer.

This substrate was oxidized in an oxygen atmosphere at 400 ° C. for 1 hour. Due to this oxidation, the inner wall of the porous Si hole was covered with the thermal oxide film. CVD (Chemical Vap) on porous Si
or Deposition) single-crystal Si was epitaxially grown by 0.15 μm. The growth conditions are as follows.

Source gas: SiH ₂ Cl ₂ / H ₂ gas flow rate: 0.5 / 180 l / min Gas pressure: 80 Torr Temperature: 950 ° C. Growth rate: 0.3 μm / min Further, the surface of this epitaxial Si layer is thermally oxidized. To form a 100 nm SiO ₂ layer.

The surface of the SiO ₂ layer and the surface of a separately prepared Si substrate (second substrate) were exposed to nitrogen plasma, respectively, superposed and contacted, and annealed at 400 ° C. for 10 hours.

When a sufficient tensile force was uniformly applied to the bonded wafers in a direction perpendicular to the plane and further in the plane, the wafers were separated in the fragile lower porous Si layer. Pressing or shearing force instead of tensile force also resulted in separation in the brittle lower porous Si layer. Further, even when a knife-like object was inserted into the gap between the edges of the bonded wafers like a wedge, the wafer was similarly separated in the fragile lower porous Si layer.

Then, the porous Si remaining on the second substrate side is removed.
The layer was selectively etched with a mixture of 49% hydrofluoric acid and 30% hydrogen peroxide while stirring. The single-crystal Si remained without being etched, and the porous Si was selectively etched and completely removed using the single-crystal Si as a material for an etch stop.

Thus, a single-crystal Si layer having a thickness of 0.1 μm was formed on the Si oxide film. When the film thickness of the formed single crystal Si layer was measured at 100 points over the entire surface in the plane, the film thickness uniformity was 101 nm ± 3 nm.

Further, a heat treatment was performed in hydrogen at 1100 ° C. for 1 hour. When the surface roughness was evaluated with an atomic force microscope, the mean square roughness in a 50 μm square area was about 0.2.
nm, which was equivalent to that of a commercially available Si wafer.

As a result of observation of a cross section by a transmission electron microscope,
No new crystal defects were introduced into the i-layer, and it was confirmed that good crystallinity was maintained.

The porous Si remaining on the first substrate side is also selectively etched while stirring with a mixed solution of 49% hydrofluoric acid and 30% hydrogen peroxide. Monocrystalline Si remained without being etched, the monocrystalline Si as an etch stopper, the porous Si was selectively etched is completely removed, a high concentration P ⁺ layer of the diffusion process as the first substrate again, Alternatively, it could be put into the bonding step as a second substrate.

(Example 16) A P ⁺ high concentration layer of 5 µm was formed on the surface layer of a single crystal Si substrate of a reclaimed wafer by the same diffusion method as in Example 1. At the same time, a P ⁺ high concentration layer was also formed on the back surface. Anodization was performed in the HF solution from the high concentration surface layer side. The anodizing conditions were as follows.

Current density: 7 (mA · cm ⁻² ) Anodizing solution: HF: H ₂ O: C ₂ H ₅ OH = 1: 1:
1 hour: 15 (min) Thickness of porous Si: 16 (μm) The obtained porous Si layer had a two-layer structure. The lower porous Si layer had a fine brittle structure compared to the surface layer.

This substrate was oxidized in an oxygen atmosphere at 400 ° C. for 1 hour. Due to this oxidation, the inner wall of the porous Si hole was covered with a thin thermal oxide film.

Then, the outermost surface of the substrate on which the porous layer was formed was immersed in a 1.25% HF solution to remove a thin oxide film formed on the outermost surface.

The substrate obtained in this way was then treated with H ₂ for 2 hours.
1050 ° C, 760To while flowing at 30 l / min
heat treatment for 1 minute under the conditions of rr and
Heat treatment was performed for 5 minutes under the condition that 50 sccm of H ₄ was added.

Next, CVD (Chemical Vap) is applied on the porous Si.
or Deposition) single-crystal Si was epitaxially grown by 0.15 μm. The growth conditions are as follows.

Source gas: SiH ₂ Cl ₂ / H ₂ gas flow rate: 0.5 / 180 l / min Gas pressure: 80 Torr Temperature: 950 ° C. Growth rate: 0.3 μm / min Further, the surface of this epitaxial Si layer is thermally oxidized. To form a 100 nm SiO ₂ layer.

The surface of the SiO ₂ layer and the surface of the separately prepared Si substrate (second substrate) were exposed to nitrogen plasma, respectively, and then superposed, brought into contact, and annealed at 400 ° C. for 10 hours.

When a sufficient tensile force was applied to the bonded wafers evenly in the direction perpendicular to the plane and further in the plane, the wafers were separated in the fragile lower porous Si layer. Pressing or shearing force instead of tensile force also resulted in separation in the brittle lower porous Si layer. Further, even when a knife-like object was inserted into the gap between the edges of the bonded wafers like a wedge, the wafer was similarly separated in the fragile lower porous Si layer.

Thereafter, the porous Si remaining on the second substrate side
The layer was selectively etched with a mixture of 49% hydrofluoric acid and 30% hydrogen peroxide while stirring. The single-crystal Si remained without being etched, and the porous Si was selectively etched and completely removed using the single-crystal Si as a material for an etch stop.

Thus, a single-crystal Si layer having a thickness of 0.1 μm was formed on the Si oxide film. When the film thickness of the formed single crystal Si layer was measured at 100 points over the entire surface in the plane, the film thickness uniformity was 101 nm ± 3 nm.

Further, a heat treatment was performed in hydrogen at 1100 ° C. for 1 hour. When the surface roughness was evaluated with an atomic force microscope, the mean square roughness in a 50 μm square area was about 0.2.
nm, which was equivalent to that of a commercially available Si wafer.

As a result of observation of a cross section by a transmission electron microscope,
No new crystal defects were introduced into the i-layer, and it was confirmed that good crystallinity was maintained.

Further, the porous Si remaining on the first substrate side is also selectively etched while stirring with a mixed solution of 49% hydrofluoric acid and 30% hydrogen peroxide. Monocrystalline Si remained without being etched, the monocrystalline Si as an etch stopper, the porous Si was selectively etched is completely removed, a high concentration P ⁺ layer of the diffusion process as the first substrate again, Alternatively, it could be put into the bonding step as a second substrate.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view for explaining a process of the present invention.

FIG. 2 is a schematic cross-sectional view for explaining a process of the present invention.

FIG. 3 is a schematic sectional view showing an example of a furnace used for forming a diffusion region.

FIG. 4 is a schematic cross-sectional view for explaining a process of a first conventional example.

FIG. 5 is a schematic cross-sectional view for explaining a process of a second conventional example.

[Description of Signs] 11 Si substrate 12 P ⁺ diffusion layer 13 P ⁺ porous Si 14 lower porous Si 15 non-porous thin film 16 second substrate 17 insulating layer 21 Si substrate 22 P ⁺ diffusion layer 23 P ⁺ porous Si 24 Lower porous Si 25 Non-porous thin film 26 Second substrate 27 Second substrate 28 Insulating layer 31 Si substrate 32 Porous Si 33 Single crystal thin film 34 Supporting substrate 35 Insulating layer 41 Si substrate 42 Porous Si 43 Single Crystal thin film 44 Support substrate 45 Insulating layer

Continuation of front page (56) References JP-A-7-302889 (JP, A) JP-A-5-109888 (JP, A) JP-A-7-176487 (JP, A) JP-A-5-217828 (JP) JP-A-8-70111 (JP, A) JP-A-9-100197 (JP, A) JP-A-5-217821 (JP, A) JP-A-5-217990 (JP, A) JP-A-5-217823 (JP, A) JP-A-62-18539 (JP, A) P. Holmstrom, et. Al. , "Complete Die Electric Isolation by Highly Selective and Self-Stopping Formation of the Oxidized Porous Silicon", Appl. Phys. Let t. , December 31, 1983, vol. 42, No. 4, pp. 386-388 L.C. VESCAN, et. al. , "LOW-PRESSURE VAPOR-PHASE EPITAXY OF SILICON ON POROUS SILICON", MATERIALS LETTERS, December 31, 1988, VOL. 7, NO. 3, pp. 94-98 Takao Abe et al., "Silicon Crystals and Doping," Second Edition, Maruzen Co., Ltd., March 25, 1988

Claims (47)

(57) [Claims] 1. The method according to claim 1 , wherein the silicon substrate has a P
Forming a P-type impurity region having a high type impurity concentration, forming a first porous silicon layer in the P-type impurity region, and forming the first porous silicon layer under the P-type impurity region where the first porous silicon layer is formed; Form a second porous silicon layer on the silicon substrate
Form, the first to the porous silicon layer to form a non-porous semiconductor layer, a step of preparing a first substrate, said said first substrate and the second substrate non-porous semiconductor layer And a separating step of separating the multilayer structure in the second porous silicon layer, wherein a bonding step is performed so that a multilayer structure positioned inside is obtained. Production method. 2. A process for producing a semiconductor article according to claim 1, wherein the bonding step is performed via an insulating layer. 3. The method for manufacturing a semiconductor member according to claim 1, further comprising a step of removing the first porous silicon layer remaining on the side of the second substrate after the separation step. After wherein said separation step, claims a portion of the silicon substrate obtained by removing the second porous silicon layer remaining on said silicon substrate, using as a raw material of the first substrate 4. The method for manufacturing a semiconductor member according to item 3 . Wherein after said separating step, claims a portion of the silicon substrate obtained by removing the second porous silicon layer remaining on said silicon substrate, using as a raw material of the second substrate 4. The method for manufacturing a semiconductor member according to item 3 . Wherein said first porous silicon layer and the second
The thickness of the layer including the porous silicon layer is 1 μm to 15 μm.
The method according to claim 1 , wherein the semiconductor member is controlled to 0 μm. 7. The first porous silicon layer and a second porous silicon layer.
The thickness of the combined layer of the porous silicon layers is 2 μm to 80 μm.
The method for manufacturing a semiconductor member according to claim 6 , wherein the thickness is controlled to μm. 8. The thickness of the porous silicon layer 5μm~
The method for manufacturing a semiconductor member according to claim 7 , wherein the thickness is controlled to 50 μm. 9. The semiconductor device according to claim 1 , wherein said P-type is provided on two surfaces of said silicon substrate.
After forming the impurity region and the first and second porous silicon layer, according to claim 1 or to form the non-porous semiconductor layer to the two formed in said surface a first porous silicon layer A method for manufacturing a semiconductor member according to claim 2 . 10. The method according to claim 1 , wherein the separating step comprises the step of :
3. The method for manufacturing a semiconductor member according to claim 1 , wherein the method is performed by applying an external force to the recon layer . 11. The semiconductor according to claim 10 , wherein the method for applying the force is selected from pressing in a direction perpendicular to the surface of the substrate, pulling in a direction perpendicular to the surface of the substrate, and applying a shearing force. Manufacturing method of the member. 12. The method of claim 11, wherein the separation step, said after expose the multilayer structure of the first porous silicon layer and / or the second porous silicon layer on the end portion of the oxide of the bonded substrates The method for manufacturing a semiconductor member according to claim 1 , wherein the method is performed. Wherein said separation of the multilayer structure, according to claim 1 or claim 2 is performed by heating the multilayer structure
3. The method for manufacturing a semiconductor member according to item 1. 14. The method for manufacturing a semiconductor member according to claim 13 , wherein said heating is for heating the entire multilayer structure. 15. The method for manufacturing a semiconductor member according to claim 13 , wherein said heating is to partially heat said multilayer structure. 16. The method according to claim 15 , wherein the heating is performed by laser irradiation. 17. The method according to claim 16 , wherein the laser is a carbon dioxide laser. 18. The method of claim 17, wherein the heating is according to claim 1 which is made by flowing the first and second current to the porous silicon layer
6. The method for manufacturing a semiconductor member according to 5 . 19. The method for manufacturing a semiconductor member according to claim 1 , wherein said non-porous semiconductor layer comprises a single-crystal silicon layer. 20. The method according to claim 19 , wherein the single crystal silicon layer is formed by epitaxial growth. 21. A first substrate comprising a silicon oxide layer formed on a surface of the single crystal silicon layer.
20. The method for manufacturing a semiconductor member according to 20 . 22. The method according to claim 21 , wherein the silicon oxide layer is formed by thermal oxidation. 23. The non-porous semiconductor layer process for producing a semiconductor article according to any one of constituted claims 1 to 5 in the compound semiconductor layer. 24. The method according to claim 23 , wherein the compound semiconductor layer forms a single crystal. 25. The process for producing a semiconductor article according to claim 1 using a single crystal silicon substrate as the second substrate. 26. A substrate in which an oxide film is formed on the surface of a single crystal silicon substrate as the second substrate .
5. The method for manufacturing a semiconductor member according to any one of items 5 . 27. The method for manufacturing a semiconductor member according to claim 1 , wherein a light transmitting substrate is used as said second substrate. 28. The method for manufacturing a semiconductor member according to claim 27 , wherein a glass substrate is used as said light transmitting substrate. 29. The bonding process is process for producing a semiconductor article according to claim 1 is made by adhering the two substrates. 30. The bonding step is anodic bonding, pressurization process for producing a semiconductor article according to claim 1, it made using a heat treatment. 31. The removal of the first and / or second porous silicon layer according to claim 3-5, made by grinding
The method for manufacturing a semiconductor member according to any one of the above. 32. The removal of the first and / or second porous silicon layers is performed by etching.
6. The method for manufacturing a semiconductor member according to any one of 3 to 5 . 33. The method according to claim 32 , wherein the etching is performed using hydrofluoric acid. 34. The first porous silicon layer and / or
Alternatively, the non-porous semiconductor layer is formed after forming an oxide film on the hole wall of the second porous silicon layer .
5. The method for manufacturing a semiconductor member according to any one of items 5 . 35. After heat treatment in an atmosphere containing hydrogen the first porous silicon layer surface, of the non-porous semiconductor article according to any one of claims 1～5,34 for forming a semiconductor layer Production method. 36. A method for forming the non-porous semiconductor layer on the first porous silicon layer, comprising the steps of: flowing a minute amount of a source gas containing silicon atoms into a film forming chamber; The method for manufacturing a semiconductor member according to any one of claims 1 to 5 , 34 , and 35 , wherein the method is formed by a step including a step of closing the hole. 37. The formation of the P-type impurity region, method of manufacturing a semiconductor article according to claim 1 made by epitaxial growth. 38. The formation of the P-type impurity region, method of manufacturing a semiconductor article according to claim 1 or claim 2 made by diffusion. 39. The method according to claim 36 , wherein the substance diffused by the diffusion method is boron. 40. The concentration of boron contained in the P-type impurity region is from 5.0 × 10 ¹⁶ / cm ^{3 to} 5.0 × 10 ^20.
The process for producing a semiconductor article according to claim 1 or claim 2 is controlled in the range of / cm ^3. 41. The concentration of boron contained in the P-type impurity region is 1.0 × 10 ¹⁷ / cm ^{3 to} 2.0 × 10 ^20.
41. The method for manufacturing a semiconductor member according to claim 40 , wherein the control is performed in a range of / cm ³ . 42. The concentration of boron contained in the P-type impurity region is from 5.0 × 10 ¹⁷ / cm ^{3 to} 1.0 × 10 ^20.
42. The method of manufacturing a semiconductor member according to claim 41 , wherein the control is performed in a range of / cm ³ . 43. The P-type impurity region has a thickness of 100
The process for producing a semiconductor article according to claim 1 or claim 2 is controlled to A～100myuemu. 44. The P-type impurity region has a thickness of 500
The process for producing a semiconductor article according to claim 1 or claim 2 is controlled to A～50myuemu. 45. The P-type impurity region has a thickness of 500
The method for manufacturing a semiconductor member according to claim 1 , wherein the semiconductor member is controlled at 0 ° to 30 μm. 46. The method of claim 45, wherein the porosity of the second porous silicon manufacturing a semiconductor article according to claim 1 is greater than the porosity of the first porous silicon layer. 47. After the separation step, producing a semiconductor article according to claim 1 or claim 2, heat treating the non-porous semiconductor layer disposed on the second substrate in an atmosphere containing hydrogen .