JP2010080834A - Method of manufacturing soi substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To reduce chipping and crack even when a semiconductor substrate is repeatedly used in a manufacturing process of an SOI substrate, or to raise use efficiency of one semiconductor substrate and to reduce the chipping and the crack, in the manufacturing process of the SOI substrate. <P>SOLUTION: In the manufacturing process of the SOI substrate, after repeatedly using the semiconductor substrate to be used as a bond substrate, several times, a laminated substrate is formed by sticking the semiconductor substrate with other second single crystal semiconductor substrate at a stage that a chamfered part of the semiconductor substrate disappears or before the chamfered part disappears, and is used as the bond substrate after forming the chamfered part on the laminate substrate. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to a method for manufacturing a substrate provided with a semiconductor layer with an insulating layer interposed therebetween, and more particularly to a method for manufacturing an SOI (Silicon on Insulator) substrate. The present invention also relates to a method of reusing (recycling) a semiconductor substrate in a manufacturing process of a substrate provided with a semiconductor layer via an insulating layer.

An SOI substrate having a semiconductor layer over a base substrate having an insulating surface has attracted attention as a substrate suitable for manufacturing a semiconductor device capable of low power consumption and high-speed operation.

As one method for manufacturing an SOI substrate, a hydrogen ion implantation separation method is known (for example, see Patent Document 1). In the hydrogen ion implantation separation method, first, an oxide film is formed on at least one of the two silicon wafers to be a bond substrate, and hydrogen ions or rare gas ions are implanted from the upper surface, and the inside of the silicon wafer To form a microbubble layer. Then, the surface into which the ions have been implanted is brought into close contact with the other silicon wafer serving as the base substrate via the oxide film, and then heat treatment is performed to separate one wafer into a thin film using the microbubble layer as a cleavage plane, Further, it is a technique in which a heat treatment is applied to firmly bond to form an SOI substrate.

In addition, in the manufacture of SOI substrates, a method of repeatedly using a silicon wafer to be a bond substrate has been studied for efficient and economical use of the silicon wafer (see, for example, Patent Document 2).

In general, silicon wafers used in the production of semiconductor devices prevent chipping and cracks by chamfering the peripheral edge of the silicon wafer (for example, Patent Document 3).
Japanese Patent Application Laid-Open No. 2000-124092 JP 2008-21892 A JP 2004-281609 A

When a chamfered semiconductor substrate is repeatedly used in the manufacturing process of an SOI substrate, the chamfered portion provided on the semiconductor substrate disappears at a certain point because the semiconductor substrate becomes thinner. When a semiconductor substrate having such a chamfered portion is used as a bond substrate in the manufacture of an SOI substrate, there is a high possibility that chipping or cracks will occur. In addition, when the use of the semiconductor substrate is stopped when the chamfered portion of the semiconductor substrate disappears, the number of times that the chamfered semiconductor substrate can be used repeatedly is limited, and it is difficult to sufficiently increase the use efficiency of the semiconductor substrate. It becomes. In manufacturing an SOI substrate, since the semiconductor substrate itself is expensive, it is important to reduce the cost by increasing the use efficiency of the semiconductor substrate.

On the other hand, when the chamfering process is performed again on the semiconductor substrate when the chamfered portion of the semiconductor substrate is lost, the semiconductor substrate is thinned because it has already been used repeatedly, and it is difficult to handle the chamfering process, and the semiconductor substrate may be damaged. is there. As a result, the use efficiency of the semiconductor substrate is lowered in the manufacturing process of the SOI substrate, and the material cost is increased.

In view of the above problems, an object of the present invention is to reduce chipping and cracks even when a semiconductor substrate is repeatedly used in a manufacturing process of an SOI substrate. Another object is to increase the use efficiency of one semiconductor substrate and reduce chipping and cracks in the manufacturing process of an SOI substrate.

According to the present invention, after a semiconductor substrate used as a bond substrate is repeatedly used a plurality of times in an SOI substrate manufacturing process, the semiconductor substrate is replaced with another second single crystal semiconductor before or after the chamfered portion of the semiconductor substrate is eliminated. A laminated substrate is formed by bonding to a substrate, and a chamfered portion is formed on the laminated substrate, and then used as a bond substrate.

One aspect of the present invention includes a front side chamfer, a back side chamfer, and an end surface that connects the front side chamfer and the back side chamfer, and the surface of the first single crystal semiconductor substrate serving as a bond substrate has ions Is irradiated to form a brittle region in the first single crystal semiconductor substrate, and the first single crystal semiconductor substrate and the base substrate are bonded to each other with the insulating layer interposed therebetween. A second step of separating one single crystal semiconductor substrate and forming a single crystal semiconductor layer over a base substrate with an insulating layer interposed therebetween; and a first single crystal separated in an embrittlement region in the second step And a third step of performing a planarization process on the semiconductor substrate. The first single crystal semiconductor substrate on which the planarization process has been performed is used again as a bond substrate a plurality of times to perform the first to third steps. The process is repeated, and the surface of the first single crystal semiconductor substrate is displayed in the third process. After the side chamfer is removed, the first single crystal semiconductor substrate is bonded to the second single crystal semiconductor substrate to form a laminated substrate, and the front side chamfered portion and the back side chamfered portion are provided on the laminated substrate. The multilayer substrate is used as a bond substrate in the first step. Note that another step can be provided between any of the first to third steps.

Another aspect of the present invention is a surface of a first single crystal semiconductor substrate that has a front side chamfer, a back side chamfer, and an end face that connects the front side chamfer and the back side chamfer, and serves as a bond substrate. A first step of forming an embrittled region in the first single crystal semiconductor substrate by irradiating ions to the first single crystal semiconductor substrate, and bonding the first single crystal semiconductor substrate and the base substrate through an insulating layer; In the second step, the first single crystal semiconductor substrate is separated and a single crystal semiconductor layer is formed over the base substrate with an insulating layer interposed therebetween; and the first step separated in the embrittlement region in the second step And a third step of performing planarization treatment on the single crystal semiconductor substrate, and the first single crystal semiconductor substrate on which the planarization treatment has been performed is used again and again as a bond substrate a plurality of times. After repeating step 3, the first single crystal semiconductor used repeatedly With the front side chamfered portion remaining, the first single crystal semiconductor substrate is bonded to the second single crystal semiconductor substrate to form a laminated substrate, and the front side chamfered portion and the back side chamfered portion are formed on the laminated substrate. After providing the portion, the laminated substrate is used as a bond substrate in the first step. Note that another step can be provided between any of the first to third steps.

According to another aspect of the present invention, the surface chamfered portion of the multilayer substrate is formed on the first inclined surface formed on the first single crystal semiconductor substrate and the first inclined surface formed on the second single crystal semiconductor substrate. The second single crystal semiconductor substrate is provided with a second inclined surface provided on the same plane as the surface, and an end face connecting the front side chamfered portion and the back side chamfered portion of the multilayer substrate is provided on the second single crystal semiconductor substrate.

In this specification, a semiconductor device refers to all devices that can function by utilizing semiconductor characteristics, and a display device, an electro-optical device, a semiconductor circuit, and an electronic device are all included in the semiconductor device.

According to the present invention, chipping and cracks can be reduced even when a semiconductor substrate is reused in a manufacturing process of an SOI substrate.

According to the present invention, the use efficiency of a single semiconductor substrate can be increased and chipping and cracks can be reduced in the manufacturing process of an SOI substrate.

Embodiments of the present invention will be described below with reference to the drawings. However, it will be readily understood by those skilled in the art that the present invention can be implemented in many different modes, and that forms and details can be changed without departing from the spirit and scope of the present invention. . Therefore, the present invention is not construed as being limited to the description of this embodiment mode. Note that in all the drawings for describing the embodiments, the same portions or portions having similar functions are denoted by the same reference numerals, and repetitive description thereof is omitted.

(Embodiment 1)
In this embodiment, an example of a method for manufacturing an SOI substrate will be described with reference to drawings.

First, a single crystal semiconductor substrate 100 used as a bond substrate and a base substrate 120 are prepared (see FIGS. 1A and 1B).

As the single crystal semiconductor substrate 100, for example, a single crystal semiconductor substrate made of a Group 14 element such as a single crystal silicon substrate, a single crystal germanium substrate, or a single crystal silicon germanium substrate can be used. A compound semiconductor substrate such as gallium arsenide or indium phosphide can also be used. As a commercially available silicon substrate, a circular substrate having a diameter of 5 inches (125 mm), a diameter of 6 inches (150 mm), a diameter of 8 inches (200 mm), a diameter of 12 inches (300 mm), and a diameter of 16 inches (400 mm) is typical. is there. Note that the shape of the single crystal semiconductor substrate 100 is not limited to a circle, and the single crystal semiconductor substrate 100 can be processed into a rectangular shape or the like.

In this embodiment, as the single crystal semiconductor substrate 100 to be a bond substrate, a chamfered substrate (having a chamfered portion) is used. By using a single crystal semiconductor substrate having a chamfered portion as a bond substrate, chipping and cracking of the single crystal semiconductor substrate can be reduced in the manufacturing process of the SOI substrate. As a result, it is possible to suppress the generation of dust and poor bonding due to chipping and cracks.

For example, as the single crystal semiconductor substrate 100, a front side chamfer 111b formed on the peripheral edge of the front surface 111, a back side chamfer 112b formed on the peripheral edge of the rear surface 112, a front side chamfer 111b, and a back side chamfer A single crystal silicon substrate provided with an end surface 113 connecting the portions 112b can be used (see FIG. 2A). The front side chamfer 111b is formed as an inclined surface that is inclined with respect to the main surface 111a of the front surface 111, and the rear side chamfered portion 112b is formed as an inclined surface that is inclined with respect to the main surface 112a of the rear surface 112. Further, the end surface 113 and the inclined surface are not necessarily flat and may be curved surfaces.

Further, the intersection angle θ1 between the main surface 111a of the front surface 111 and the inclined surface constituting the front surface side chamfered portion 111b, and the crossing angle θ2 between the main surface 112a of the back surface 112 and the inclined surface constituting the rear surface side chamfered portion 112b are It can be set appropriately. θ1 and θ2 may be the same or different.

As the base substrate 120, for example, a substrate made of an insulator can be used. Specific examples include various glass substrates, quartz substrates, ceramic substrates, and sapphire substrates used in the electronics industry such as aluminosilicate glass, aluminoborosilicate glass, and barium borosilicate glass. In addition, a single crystal semiconductor substrate (for example, a single crystal silicon substrate) or a polycrystalline semiconductor substrate (for example, a polycrystalline silicon substrate) may be used as the base substrate 120. A polycrystalline silicon substrate is advantageous in that it is cheaper than a single crystal silicon substrate and has higher heat resistance than a glass substrate.

Next, an embrittled region 104 having a damaged crystal structure is formed from the surface 111 of the single crystal semiconductor substrate 100 to a predetermined depth, and then the single crystal semiconductor substrate 100 and the base substrate 120 are bonded to each other with the insulating layer 102 interposed therebetween. Bonding is performed (see FIG. 1C). Here, bonding is performed so that the main surface 111 a of the surface 111 of the single crystal semiconductor substrate 100 faces the base substrate 120.

The embrittlement region 104 can be formed by irradiating the single crystal semiconductor substrate 100 with ions such as hydrogen.

The insulating layer 102 can be formed using a single layer or a stacked layer of insulating layers such as a silicon oxide film, a silicon oxynitride film, a silicon nitride film, and a silicon nitride oxide film. These films can be formed using a thermal oxidation method, a CVD method, a sputtering method, or the like.

In the present specification, silicon oxynitride has a composition containing more oxygen than nitrogen, and preferably Rutherford Backscattering Spectroscopy (RBS) and Hydrogen Forward Scattering ( When measured using HFS (Hydrogen Forward Scattering), the concentration ranges from 50 to 70 atomic% for oxygen, 0.5 to 15 atomic% for nitrogen, 25 to 35 atomic% for silicon, and 0.1 to 10 for hydrogen. It is included in the atomic% range. Further, silicon nitride oxide has a composition containing more nitrogen than oxygen, and preferably has a concentration range of 5 to 30 atomic% when measured using RBS and HFS. Nitrogen is contained in the range of 20 to 55 atomic%, silicon is contained in the range of 25 to 35 atomic%, and hydrogen is contained in the range of 10 to 30 atomic%. However, when the total number of atoms constituting silicon oxynitride or silicon nitride oxide is 100 atomic%, the content ratio of nitrogen, oxygen, silicon, and hydrogen is included in the above range.

Next, heat treatment is performed to separate the single crystal semiconductor substrate 100 in the embrittled region 104, whereby the single crystal semiconductor layer 124 is provided over the base substrate 120 with the insulating layer 102 interposed therebetween (see FIG. 1D).

By performing the heat treatment, the added element is precipitated in the minute holes formed in the embrittled region 104 due to the temperature rise, and the internal pressure rises. As the pressure rises, volume changes occur in minute holes in the embrittled region 104 and cracks occur in the embrittled region 104, so that the single crystal semiconductor substrate 100 is separated along the embrittled region 104. Since the insulating layer 102 is bonded to the base substrate 120, a single crystal semiconductor layer 124 separated from the single crystal semiconductor substrate 100 is formed over the base substrate 120.

For this heat treatment, a diffusion furnace, a heating furnace such as a resistance heating furnace, an RTA (Rapid Thermal Annealing) apparatus, a microwave heating apparatus, or the like can be used. For example, when an RTA apparatus is used, heating can be performed at a heating temperature of 550 ° C. or higher and 730 ° C. or lower and a processing time of 0.5 minutes or longer and within 60 minutes.

Through the above steps, as illustrated in FIG. 1D, an SOI substrate including the single crystal semiconductor layer 124 over the base substrate 120 with the insulating layer 102 interposed therebetween can be manufactured.

Next, the separated single crystal semiconductor substrate 100 is reused in the manufacturing process of the SOI substrate. A method for reusing the single crystal semiconductor substrate 100 will be described with reference to FIGS.

First, planarization treatment is performed on the separated single crystal semiconductor substrate 100 (see FIG. 1E-1). Here, planarization treatment is performed on at least the main surface 111a of the surface 111 of the single crystal semiconductor substrate 100 which is a separation surface. By performing the planarization treatment, the main surface 111a of the surface 111 of the single crystal semiconductor substrate 100 after separation can be planarized, and the single crystal semiconductor substrate 100 can be reused as a bond substrate.

As the planarization treatment, wet etching treatment can be performed on the single crystal semiconductor substrate 100 after separation. Thereby, the level difference of the separation surface of the single crystal semiconductor substrate 100 can be reduced. In addition, the semiconductor layer formed on the separation surface of the single crystal semiconductor substrate 100 and having crystal defects can be removed. Note that dry etching may be performed instead of wet etching, or wet etching and dry etching may be combined.

An organic alkaline aqueous solution can be used for the etchant used in the wet etching process. For example, as an organic alkaline aqueous solution, an aqueous solution containing 0.2 to 5.0% of TMAH (Tetra Methyl Ammonium Hydroxide, tetramethylammonium hydroxide) (for example, trade name: NMD3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) may be used. preferable. Moreover, it is preferable that the liquid temperature of organic alkali aqueous solution shall be 40 to 70 degreeC. More preferably, the liquid temperature is about 50 ° C. This wet etching is preferably performed for 30 seconds to 600 seconds. More preferably, the processing time is about 60 seconds.

In the case of performing wet etching, it is preferable to immerse the separated single crystal semiconductor substrate 100 in a solution in a treatment tank. In this case, an effect that a plurality of single crystal semiconductor substrates 100 can be collectively processed is obtained.

Although not illustrated, an oxide film may be formed on the surface of the single crystal semiconductor substrate 100 after wet etching, and the oxide film may be removed after the formation. By the formation of this oxide film, the effect that the single crystal semiconductor substrate 100 is dehydrogenated can be obtained. In the manufacturing process of the SOI substrate, since a large amount of hydrogen ions may be contained from the separation surface of the single crystal semiconductor substrate 100 to a depth of about 500 nm, it is effective to perform the dehydrogenation treatment. In particular, in forming the oxide film, it is preferable to thermally oxidize by adding a gas containing halogen. In this case, the gettering effect of metal impurities by atoms can be obtained. Further, metal impurities and the like taken into the oxide film can be removed by removing the oxide film.

In the planarization treatment, the main surface 111 a of the surface 111 of the single crystal semiconductor substrate 100 may be polished. As a polishing method, a chemical mechanical polishing (CMP method) can be used. The CMP method is a method in which the surface of a workpiece is used as a reference, and the surface is planarized by a combined chemical and mechanical action accordingly. In the CMP method, a polishing cloth is generally attached on a polishing stage, and the polishing stage and the workpiece are rotated or oscillated while supplying slurry (abrasive) between the workpiece and the polishing cloth. . The surface of the workpiece is polished by a chemical reaction between the slurry and the surface of the workpiece and mechanical polishing between the polishing cloth and the workpiece.

In this embodiment, it is preferable that the single crystal semiconductor substrate 100 after separation be thinned by about 1 μm to 15 μm by performing the above planarization treatment.

After that, the planarized single crystal semiconductor substrate 100 is reused as a bond substrate in the SOI substrate manufacturing process, and after repeating FIGS. 1A to 1E again (FIG. 1 ( A), (B), (C), (D), and (E-1)), the thin single crystal semiconductor substrate 100 is bonded to another single crystal semiconductor substrate 150, and the stacked substrate 200 is formed. (See FIGS. 1E-2, 2B, and 2C).

For example, after the single crystal semiconductor substrate 100 is separated, the single crystal semiconductor substrate 100 is reused as a bond substrate in the manufacturing process of an SOI substrate up to the (n-1) th (n is a natural number of 2 or more). ) To FIG. 1E-1 are performed n times, and then the single crystal semiconductor substrate 100 planarized by the n-th planarization process is bonded to another single crystal semiconductor substrate 150 to form the multilayer substrate 200. Can be formed.

As another single crystal semiconductor substrate 150, a substrate whose front and back surfaces are chamfered (having a chamfered portion), a substrate having a chamfered portion on one of the front and back surfaces, or a substrate having no chamfered portion is used. it can. In FIG. 2, as the single crystal semiconductor substrate 150, a front side chamfer 151b formed at the peripheral edge of the front surface 151, a back side chamfer 152b formed at the peripheral edge of the back surface 152, a front side chamfer 151b, and the back surface The case where a single crystal silicon substrate provided with an end face 153 connecting the side chamfered portions 152b is shown.

The number of times the single crystal semiconductor substrate 100 is reused as a bond substrate (timing to attach the single crystal semiconductor substrate 100 to another single crystal semiconductor substrate 150) is determined by the state of the surface side surface chamfer 111b of the single crystal semiconductor substrate 100. be able to.

For example, in the process of repeatedly performing FIGS. 1A to 1E-1, the first single crystal semiconductor substrate 100 is removed when the surface side surface chamfer 111b of the single crystal semiconductor substrate 100 disappears after the planarization process. Can be attached to the second single crystal semiconductor substrate 150 to form the stacked substrate 200.

Alternatively, a structure may be employed in which the single crystal semiconductor substrate 100 is bonded to another single crystal semiconductor substrate 150 before the side surface chamfer 111b of the single crystal semiconductor substrate 100 disappears. By bonding with another single crystal semiconductor substrate 150 with a margin before the surface side chamfer 111b of the single crystal semiconductor substrate 100 disappears, chipping and cracking of the single crystal semiconductor substrate 100 used repeatedly as a bond substrate can be prevented. It is because it can reduce more effectively.

Note that the stage where the surface side surface chamfered portion 111b disappears refers to a case where the main surface 111a and the end surface 113 of the surface 111 of the single crystal semiconductor substrate 100 intersect with each other (see FIG. 10A). Specifically, when the surface 111 of the single crystal semiconductor substrate 100 is circular refers the radius _{r a} of the main surface 111a, the step of maximum radius _{r max} of the single crystal semiconductor substrate 100 becomes substantially the same (See FIG. 10B). Note that the maximum radius r _max of the single crystal semiconductor substrate 100 refers to the distance from the center of the surface of the single crystal semiconductor substrate 100 to the end surface 113. Further, when the surface 111 of the single crystal semiconductor substrate 100 is rectangular, the length of the perpendicular from the center of the surface 111 of the single crystal semiconductor substrate 100 to a certain side constituting the main surface 111a and the perpendicular to the end surface 113 This refers to the stage where the lengths are approximately the same. Even when the front side chamfer 111b, the back side chamfer 112b, and the end surface 113 have curved surfaces, the stage at which the front side chamfer 111b disappears can be similarly determined (FIG. 10C).

As described above, in the manufacturing process of the SOI substrate, the single crystal semiconductor substrate 100 in which the surface chamfered portion 111b is eliminated is not used as the bond substrate, so that the single crystal semiconductor substrate is repeatedly used in the manufacturing process of the SOI substrate. Even in this case, chipping and cracking of the bond substrate can be suppressed.

Next, a chamfering process is performed on the multilayer substrate 200 to form a front side chamfer 201b and a back side chamfer 202b (see FIG. 1E-3). Thereafter, the chamfered laminated substrate 200 can be used as a bond substrate in an SOI substrate manufacturing process.

In FIG. 1E-3, the chamfered portion formed in the stacked substrate 200 is obtained by attaching the single crystal semiconductor substrate 100 and the single crystal semiconductor substrate 150 to each other after the single crystal semiconductor substrate 100 is attached to another single crystal semiconductor substrate 150. It can be provided by processing. For example, by chamfering the single crystal semiconductor substrate 100 after bonding it to another single crystal semiconductor substrate 150, the surface side chamfer 201b, the back side chamfer 202b, and the surface side chamfer 201b It can be set as the structure which provided the end surface 203 which connects the back surface side part 202b (refer FIG.1 (E-3) and FIG.2 (D)).

For example, the surface side chamfer 201b of the multilayer substrate 200 is formed on the same plane as the first inclined surface 211 formed on the single crystal semiconductor substrate 100 and the first inclined surface 211 formed on the single crystal semiconductor substrate 150. The second inclined surface 212 is provided, the end surface 203 of the multilayer substrate 200 is provided on the single crystal semiconductor substrate 150, and the back side chamfer 202 b of the multilayer substrate 200 is formed on the single crystal semiconductor substrate 150. The surface 213 can be provided.

In this case, the first inclined surface 211 intersects the main surface 111 a and the back main surface 112 a of the front surface 111 of the single crystal semiconductor substrate 100, and the second inclined surface 212 is the main surface of the surface of the single crystal semiconductor substrate 150. It intersects with the surface 151a and the end surface 153. Further, the surface side chamfer 201b includes a bonded interface between the single crystal semiconductor substrate 100 and the single crystal semiconductor substrate 150. As described above, the surface side chamfer 201b of the multilayer substrate 200 is formed of the first inclined surface 211 and the second inclined surface 212 that are located on the same surface, whereby the single crystal semiconductor substrate 100 and the single crystal semiconductor substrate are formed. The step of the bonding interface 150 can be reduced, and chipping and cracks of the multilayer substrate 200 can be reduced.

The third inclined surface 213 intersects the main surface 152 a and the end surface 153 of the back surface 152 of the single crystal semiconductor substrate 150.

Note that in the case where the single-crystal semiconductor substrate 150 is provided with the back surface side chamfer 152 b in advance, the back surface side chamfer 202 b of the multilayer substrate 200 can be provided by the back surface side chamfer 152 b of the single crystal semiconductor substrate 150. . In this case, the process of forming the back surface side chamfer of the laminated substrate 200 can be omitted.

Further, in the chamfering process of FIG. 1E-3, the end surface 203 that connects the front side chamfered portion 201b and the rear side chamfered portion 202b is formed between the single crystal semiconductor substrate 100 and the single crystal semiconductor substrate 150 constituting the stacked substrate 200. Of these, it is preferable to provide one of the substrates. By providing the end surface 203 on one substrate (here, the single crystal semiconductor substrate 150), when the laminated substrate 200 is repeatedly used as a bond substrate until the chamfered portion disappears, the other substrate (here, the chamfered portion disappears) Then, the single crystal semiconductor substrate 100) can be used up. As a result, when the multilayer substrate is formed again, one bonding interface can be provided on the multilayer substrate.

In the case where the single crystal semiconductor substrate 100 and the single crystal semiconductor substrate 150 have different thicknesses, the end surface 203 is preferably formed on the thicker single crystal semiconductor substrate (here, the single crystal semiconductor substrate 150) side. By providing the end surface 203 on the thicker single crystal semiconductor substrate side, the width for forming the end surface 203 can be easily adjusted, so that the shape of the chamfered portion can be easily formed into a desired shape.

Further, in the case where there is no significant difference in thickness between the single crystal semiconductor substrate 100 and the single crystal semiconductor substrate 150, the end surface 203 may be provided over both the single crystal semiconductor substrates. In this case, the end surface of the multilayer substrate 200 includes a bonded interface between the single crystal semiconductor substrate 100 and the single crystal semiconductor substrate 150.

As described above, in this embodiment, instead of discarding the single crystal semiconductor substrate 100 thinned by reuse, the multilayer substrate 200 is formed by being bonded to another single crystal semiconductor substrate 150, and the multilayer substrate 200. Is reused as a bond substrate. In this case, in the manufacturing process of the SOI substrate, the single crystal semiconductor substrate 100 can be used without waste until the end, and the use efficiency of one single crystal semiconductor substrate can be improved. As a result, cost reduction can be achieved in the manufacturing process of the SOI substrate.

In addition, before or after the surface side chamfer 111b of the single crystal semiconductor substrate 100 is eliminated, the single crystal semiconductor substrate 100 is bonded to another single crystal semiconductor substrate 150 to form the multilayer substrate 200. By using it as a bond substrate after forming the chamfered portion, chipping and cracks can be reduced even when the bond substrate is reused.

In addition, even when the single crystal semiconductor substrate 100 is repeatedly used and thinned, the thin single crystal semiconductor substrate 100 is bonded to another single crystal semiconductor substrate 150 to perform chamfering. In some cases, the single crystal semiconductor substrate 100 can be prevented from being damaged, and the single crystal semiconductor substrate 100 can be reused as a part of the bond substrate. Thereby, the material cost in the SOI manufacturing process can be kept low.

Note that in the SOI substrate manufacturing process illustrated in FIG. 1, the single crystal semiconductor substrate 100 and the single crystal semiconductor substrate 150 may be bonded to each other by directly bonding the single crystal semiconductor substrates to each other or via an insulating layer. The crystal semiconductor substrate 100 and the single crystal semiconductor substrate 150 may be bonded. A method for manufacturing the stacked substrate 200 by bonding the single crystal semiconductor substrate 100 and the single crystal semiconductor substrate 150 is described below with reference to drawings.

FIG. 4 shows a case where the single crystal semiconductor substrate 100 and the single crystal semiconductor substrate 150 are directly bonded to form the stacked substrate 200. Although a case where the main surface 112a of the back surface 112 of the single crystal semiconductor substrate 100 and the main surface 151a of the front surface 151 of the single crystal semiconductor substrate 150 are directly bonded is shown here, the present invention is not limited to this. Alternatively, as illustrated in FIGS. 1 to 3, the main surface 111 a of the surface 111 of the single crystal semiconductor substrate 100 and the main surface 151 a of the surface 151 of the single crystal semiconductor substrate 150 may be directly bonded.

First, the single crystal semiconductor substrate 100 and the single crystal semiconductor substrate 150 are prepared (see FIGS. 4A-1 and 4B-1). Note that the bonded surface of the single crystal semiconductor substrate 100 and the single crystal semiconductor substrate 150 is preferably polished and planarized in advance. As the single crystal semiconductor substrate 150, for example, a single crystal semiconductor substrate made of a Group 14 element such as a single crystal silicon substrate, a single crystal germanium substrate, or a single crystal silicon germanium substrate can be used. In addition, the use of a substrate made of the same material as the single crystal semiconductor substrate 100 as the single crystal semiconductor substrate 150 does not change the thermal expansion coefficient and the like, so that bonding defects can be suppressed.

Next, after surface treatment is performed on one or both of the bonding surface of the single crystal semiconductor substrate 100 and the bonding surface of the single crystal semiconductor substrate 150 (see FIGS. 4A-2 and 4B-2), The main surface 112a of the back surface 112 of the single crystal semiconductor substrate 100 and the main surface 151a of the front surface 151 of the single crystal semiconductor substrate 150 are joined to form the stacked substrate 200 (see FIG. 4C).

Here, as the surface treatment, the surface of the single crystal semiconductor substrate 100 and the surface of the single crystal semiconductor substrate 150 are irradiated with a fast atomic beam of argon (Ar) in a vacuum to activate the surfaces, and then bonded at room temperature as they are. The case (vacuum bonding) is shown. In addition, as the surface treatment, a hydroxyl group is introduced by performing wet treatment on one or both of the surface of the single crystal semiconductor substrate 100 and the surface of the single crystal semiconductor substrate 150, and a hydrogen bond between the hydroxyl groups is used. And may be joined. In this case, heat treatment may be performed to improve the bonding strength.

FIG. 5 illustrates the case where the stacked substrate 200 is manufactured by bonding the single crystal semiconductor substrate 100 and the single crystal semiconductor substrate 150 through an insulating layer functioning as a bonding layer. Here, a case is shown in which the main surface 111a of the surface 111 of the single crystal semiconductor substrate 100 and the main surface 151a of the surface 151 of the single crystal semiconductor substrate 150 are bonded to each other, but the present invention is not limited to this. In addition, the main surface 112a of the back surface 112 of the single crystal semiconductor substrate 100 and the main surface 151a of the front surface 151 of the single crystal semiconductor substrate 150 may be bonded to each other.

First, after preparing the single crystal semiconductor substrate 100 and the single crystal semiconductor substrate 150 (see FIGS. 5A-1 and 5B), at least a bonding surface of the single crystal semiconductor substrate 100 (here, the surface 111) An insulating layer 142 serving as a bonding layer is formed on the main surface 111a).

As the insulating layer 142, for example, a single layer such as a silicon oxide film, a silicon oxynitride film, a silicon nitride film, or a silicon nitride oxide film, or a film in which these layers are stacked can be used. These films can be formed using a thermal oxidation method, a CVD method, a sputtering method, or the like. Here, a case is shown in which an insulating layer 142 (eg, a SiOx film) is formed on the front surface 111 and the back surface 112 of the single crystal semiconductor substrate 100 by performing thermal oxidation treatment (see FIG. 5A-2).

Note that the thermal oxidation treatment is preferably performed by adding halogen in an oxidizing atmosphere. For example, the single crystal semiconductor substrate 100 is subjected to thermal oxidation treatment in an oxidizing atmosphere to which chlorine (Cl) is added, so that the insulating layer 142 subjected to chlorine oxidation is formed. In this case, the insulating layer 142 is a film containing chlorine atoms. The inclusion of chlorine in the insulating layer 142 has an effect of gettering a metal that becomes an impurity.

Next, the surface 111 of the single crystal semiconductor substrate 100 and the surface 151 of the single crystal semiconductor substrate 150 are opposed to each other, and the surface of the insulating layer 142 and the main surface 151a of the surface 151 of the single crystal semiconductor substrate 150 are bonded to each other. 200 is formed (see FIG. 5C). In addition, after the surface of the insulating layer 142 and the main surface 151a of the surface 151 of the single crystal semiconductor substrate 150 are bonded, heat treatment for increasing the bonding strength is preferably performed.

Next, a front side chamfer and a back side chamfer are provided on the multilayer substrate 200 (see FIG. 5D). Here, the front side chamfer 201b of the multilayer substrate 200 includes the first inclined surface 211 that intersects the main surface 111a and the back main surface 112a of the surface 111 of the single crystal semiconductor substrate 100, and the surface of the single crystal semiconductor substrate 150. The second inclined surface 212 that intersects the main surface 151a and the end surface 153 of the first surface and is provided on the same plane as the first inclined surface 211, and is provided between the first inclined surface 211 and the second inclined surface 212. And the insulating layer 142 formed.

Further, by selectively etching the insulating layer 142, the insulating layer 142 is left between the single crystal semiconductor substrate 100 and the single crystal semiconductor substrate 150, and the insulating layer 142 formed on the surface of the stacked substrate 200 is removed. May be.

Further, in the case where the insulating layer 142 is formed over the entire surface of the single crystal semiconductor substrate 100 using a thermal oxidation method, the insulating layer 142 is formed without removing the insulating layer 142 formed over the main surface 201a of the surface of the stacked substrate 200. Bonding with the base substrate 120 may be performed via In this case, the step of removing the insulating layer 142 and the step of forming the insulating layer 102 can be omitted, and the manufacturing process of the SOI substrate can be simplified.

Note that FIG. 5 illustrates the case where bonding is performed by providing the insulating layer 142 which serves as a bonding layer on the surface of the single crystal semiconductor substrate 100, but the single crystal semiconductor substrate 150 is provided with the insulating layer 142. The surface of the semiconductor substrate 100 and the surface of the insulating layer 142 may be bonded.

FIG. 6 illustrates the case where an insulating layer functioning as a bonding layer is provided on the surface of each of the single crystal semiconductor substrate 100 and the single crystal semiconductor substrate 150 and the stacked substrate 200 is formed by bonding the insulating layers to each other. Here, a case where a substrate that is not chamfered is used as the single crystal semiconductor substrate 150 and the main surface 111a of the surface 111 of the single crystal semiconductor substrate 100 and the surface 151 of the single crystal semiconductor substrate 150 are bonded to each other is shown. However, it is not limited to this. In addition, the main surface 112 a of the back surface 112 of the single crystal semiconductor substrate 100 and the front surface 151 of the single crystal semiconductor substrate 150 may be bonded to each other.

First, after preparing the single crystal semiconductor substrate 100 and the single crystal semiconductor substrate 150 (see FIGS. 6A-1 and 6B-1), at least a bonding surface of the single crystal semiconductor substrate 100 (here, the surface 111). An insulating layer 144 serving as a bonding layer is formed over the main surface 111a), and an insulating layer 146 serving as a bonding layer is formed over the bonding surface (here, the surface 151) of the single crystal semiconductor substrate 150.

As the insulating layer 144 and the insulating layer 146, for example, a single layer such as a silicon oxide film, a silicon oxynitride film, a silicon nitride film, or a silicon nitride oxide film, or a film in which these layers are stacked can be used. These films can be formed using a thermal oxidation method, a CVD method, a sputtering method, or the like. Here, a case is shown in which an insulating layer 144 and an insulating layer 146 (for example, a SiOx film) are formed over the single crystal semiconductor substrate 100 and the single crystal semiconductor substrate 150, respectively, by performing thermal oxidation treatment (FIG. 6A). -2) and (B-2)). Note that the thermal oxidation treatment may be performed by adding halogen in an oxidizing atmosphere.

The insulating layer 144 and the insulating layer 146 may be formed using the same material or different materials.

Next, the surface 111 of the single crystal semiconductor substrate 100 and the surface 151 of the single crystal semiconductor substrate 150 are opposed to each other, and the surface of the insulating layer 144 and the surface of the insulating layer 146 are bonded to form the stacked substrate 200 (FIG. 6). (See (C)). In addition, after the surface of the insulating layer 144 and the surface of the insulating layer 146 are bonded, heat treatment for increasing the bonding strength is preferably performed.

Next, a front side chamfer 201b and a back side chamfer 202b are provided on the multilayer substrate 200 (see FIG. 6D). Here, the front side chamfer 201b of the multilayer substrate 200 includes the first inclined surface 211 that intersects the main surface 111a and the back main surface 112a of the surface 111 of the single crystal semiconductor substrate 100, and the surface of the single crystal semiconductor substrate 150. 151 and the end surface 153 and the second inclined surface 212 provided on the same plane as the first inclined surface 211, and the insulation provided between the first inclined surface 211 and the second inclined surface 212 A layer 144 and an insulating layer 146 are formed.

In addition, by selectively etching the insulating layer 144 and the insulating layer 146, the insulating layer 144 and the insulating layer 146 are left between the single crystal semiconductor substrate 100 and the single crystal semiconductor substrate 150 and are formed on the surface of the stacked substrate 200. The insulating layer 144 may be removed.

Further, in the case where the insulating layer 144 is formed over the entire surface of the single crystal semiconductor substrate 100 using a thermal oxidation method, the insulating layer 144 is formed without removing the insulating layer 144 formed over the main surface 201a of the surface of the stacked substrate 200. Bonding with the base substrate 120 may be performed via In this case, the step of removing the insulating layer 144 and the step of forming the insulating layer 102 can be omitted, and the manufacturing process of the SOI substrate can be simplified.

4 to 6, as the single crystal semiconductor substrate 150, a substrate repeatedly used in the manufacturing process of an SOI substrate may be used (see FIG. 9). FIG. 9 illustrates a case where a thin single crystal semiconductor substrate which is repeatedly used as the single crystal semiconductor substrate 150 in FIG. 4 is used.

Similarly to FIG. 4, after the single crystal semiconductor substrate 100 and the single crystal semiconductor substrate 150 are bonded to each other to form the multilayer substrate 200 (see FIGS. 9A-1 to 9C), the multilayer substrate 200 is chamfered. By doing so, a front side chamfer 201b and a back side chamfer 202b can be formed (see FIG. 9D).

In the chamfering process, it is preferable that an end surface 203 that connects the front side chamfered portion 201b and the back side chamfered portion 202b is provided on one of the single crystal semiconductor substrate 100 and the single crystal semiconductor substrate 150 constituting the stacked substrate 200. . By providing the end surface 203 on one substrate, when the laminated substrate 200 is repeatedly used as a bond substrate until the chamfered portion disappears, the other substrate can be used up before the chamfered portion disappears. As a result, when the multilayer substrate is formed again, one bonding interface can be provided on the multilayer substrate.

In the case where the single crystal semiconductor substrate 100 and the single crystal semiconductor substrate 150 have different thicknesses, the end surface 203 is preferably formed on the thicker single crystal semiconductor substrate side. This is because by providing the end surface 203 on the thicker single crystal semiconductor substrate side, the width for forming the end surface 203 can be easily adjusted, so that the shape of the chamfered portion formed on the thick substrate side can be easily processed into a desired shape. . Note that in the case where there is no significant difference in thickness between the single crystal semiconductor substrate 100 and the single crystal semiconductor substrate 150, the end surface 203 may be provided over both single crystal semiconductor substrates. In this case, the end surface of the multilayer substrate includes a bonded interface between the single crystal semiconductor substrate 100 and the single crystal semiconductor substrate 150.

Note that FIG. 9 illustrates the case where the main surface 111 a of the surface 111 of the single crystal semiconductor substrate 100 and the main surface 151 a of the surface 151 of the single crystal semiconductor substrate 150 are bonded to each other, but the present invention is not limited thereto. The main surface 111a of the front surface 111 of the single crystal semiconductor substrate 100 and the main surface 152a of the back surface 152 of the single crystal semiconductor substrate 150 may be bonded together, or the main surface 112a of the back surface 112 of the single crystal semiconductor substrate 100 and the single crystal semiconductor substrate The main surface 151a of the surface 151 of 150 may be bonded, or the main surface 112a of the back surface 112 of the single crystal semiconductor substrate 100 and the main surface 152a of the back surface 152 of the single crystal semiconductor substrate 150 may be bonded.

In addition, it is preferable to perform bonding so that the back surface side of any one single crystal semiconductor substrate is disposed on the back surface side of the multilayer substrate 200. In this case, the process of forming the back surface side chamfer of the laminated substrate 200 can be omitted.

As described above, by performing the steps described in this embodiment mode, the thickness of the regenerated single crystal semiconductor substrate is reduced, and the single crystal semiconductor substrate alone cannot be used in the manufacturing process of the SOI substrate. Even in such a case, since it can be used in the manufacturing process of an SOI substrate by being attached to another single crystal semiconductor substrate, the use efficiency of one single crystal semiconductor substrate can be increased. Thereby, cost reduction in the manufacturing process of the SOI substrate can be achieved.

Note that in the SOI substrate obtained by the manufacturing process of the SOI substrate described in this embodiment, the surface of the single crystal semiconductor layer 124 is planarized (see FIG. 1F-1), and then the single crystal semiconductor The layer 124 can be used for manufacturing a semiconductor device including a transistor or the like (see FIG. 1F-2).

Note that the structure described in this embodiment can be combined as appropriate with any of the structures described in the other embodiments in this specification.
(Embodiment 2)
In this embodiment mode, a case where an inspection process is newly provided in the manufacturing process of the SOI substrate shown in Embodiment Mode 1 will be described with reference to the drawings.

FIG. 3 shows the state of the single crystal semiconductor substrate 100 after the planarization treatment in determining the number of times the single crystal semiconductor substrate 100 is reused as a bond substrate in the SOI substrate manufacturing process shown in FIG. The case where the inspection process is provided is shown. 3 has a configuration in which an inspection process is added to FIG.

In the inspection process, the state of the single crystal semiconductor substrate 100 is inspected. For example, the periphery of the surface 111 of the single crystal semiconductor substrate 100 is observed, and the state of the surface side chamfer 111b is observed. Further, the thickness and warpage amount of the single crystal semiconductor substrate 100 may be measured. The thickness and the amount of warpage of the single crystal semiconductor substrate 100 can be measured using a laser displacement meter. In addition, observation of the surface state of the single crystal semiconductor substrate 100 can be performed using a microscope or the like.

When the surface side chamfered portion 111b of the single crystal semiconductor substrate 100 remains sufficiently as a result of the inspection, the single crystal semiconductor substrate 100 is reused as a bond substrate, and the surface side chamfered portion 111b disappears. In some cases or when it is confirmed that the substrate does not remain sufficiently, a structure in which the substrate is bonded to another single crystal semiconductor substrate 150 can be used (see FIG. 3E-2). Note that in determining whether or not to reuse the single crystal semiconductor substrate 100 as a bond substrate, not only the state of the surface side surface chamfer 111b of the single crystal semiconductor substrate 100 but also the thickness and warpage of the single crystal semiconductor substrate 100 are determined. It can be determined according to the amount, surface condition and the like.

Note that FIG. 3 illustrates the case where the main surface 111a of the surface 111 of the single crystal semiconductor substrate 110 and the main surface 151a of the surface 151 of the single crystal semiconductor substrate 150 are bonded to each other, but the present invention is not limited thereto. Absent. The main surface 112a of the back surface 112 of the single crystal semiconductor substrate 110 may be bonded to the main surface 151a of the front surface 151 of the single crystal semiconductor substrate 150 so as to face each other. In FIG. 3, as the single crystal semiconductor substrate 150, a front side chamfer 151b formed on the peripheral edge of the front surface 151, a back side chamfer 152b formed on the peripheral edge of the back surface 152, and a front side chamfer 151b. In this case, a substrate provided with an end face 153 that connects the back side chamfered portion 152b is used, but one or both of the front side chamfered portion 151b and the back side chamfered portion 152b of the single crystal semiconductor substrate 150 are provided. No substrate may be used.

3 illustrates the case where the inspection process is performed after the planarization process is performed on the single crystal semiconductor substrate 100, the inspection process may be performed before the planarization process is performed.

By providing the inspection step, the number of times the single crystal semiconductor substrate 100 is reused as a bond substrate (whether it is reused as a bond substrate or bonded to another single crystal semiconductor substrate) can be appropriately determined. As a result, generation of chipping and cracks in the manufacturing process of the SOI substrate can be suppressed, and the use efficiency of the single crystal semiconductor substrate 100 can be increased.

Note that the structure described in this embodiment can be combined as appropriate with any of the structures described in the other embodiments in this specification.
(Embodiment 3)
In this embodiment mode, refer to drawings for the case where the stacked substrate 200 in which the single crystal semiconductor substrate 100 and the single crystal semiconductor substrate 150 are bonded to each other in the above embodiment mode is used as a bond substrate in an SOI substrate manufacturing process. I will explain.

First, a stacked substrate 200 used as a bond substrate and a base substrate 120 are prepared (see FIGS. 7A and 7B). Here, the case where the single crystal semiconductor substrate 100 and the single crystal semiconductor substrate 150 which are bonded to each other with the insulating layer 142 interposed therebetween is used as the stacked substrate 200, but as illustrated in FIG. A stacked substrate in which the single crystal semiconductor substrate 150 is directly bonded may be used.

Next, an embrittled region 104 whose crystal structure is damaged to a predetermined depth from the surface of the multilayer substrate 200 is formed, and then the multilayer substrate 200 and the base substrate 120 are bonded together via the insulating layer 102 (FIG. 7). (See (C)). Here, the embrittlement region 104 is provided in the single crystal semiconductor substrate 100. Note that as described in FIG. 5 above, in the case where the insulating layer 142 formed over the entire surface of the single crystal semiconductor substrate 100 is left, the stacked substrate 200 and the base substrate 120 are bonded to each other with the insulating layer 142 interposed therebetween. It can be carried out.

Next, heat treatment is performed to separate the stacked substrate 200 in the embrittled region 104, whereby the single crystal semiconductor layer 124 is provided over the base substrate 120 with the insulating layer 102 interposed therebetween (see FIG. 7D).

Through the above steps, as illustrated in FIG. 7D, an SOI substrate including the single crystal semiconductor layer 124 over the insulating layer 102 can be manufactured over the base substrate 120. Note that after the surface of the single crystal semiconductor layer 124 is planarized (see FIG. 7F-1), the obtained SOI substrate is used for a semiconductor device including a transistor or the like using the single crystal semiconductor layer 124. It can be used for manufacturing (see FIG. 7F-2).

Next, a planarization process is performed on the stacked substrate 200 after separation (see FIG. 7E-1). Here, planarization treatment is performed on at least the surface 201 of the multilayer substrate 200 which is a separation surface. Accordingly, the surface of the laminated substrate 200 after separation (here, the front surface or the back surface of the single crystal semiconductor substrate 100) is flattened, and the laminated substrate 200 can be reused as a bond substrate in an SOI substrate manufacturing process. .

Next, the stacked substrate 200 that has been subjected to the planarization process is inspected as to whether it can be used as a bond substrate in the SOI substrate manufacturing process (see FIG. 6E-2).

In the multilayer substrate 200, defects and the like are likely to exist near the interface where the single crystal semiconductor substrate 100 and the single crystal semiconductor substrate 150 are bonded to each other, and a portion having defects near the bonded interface is provided as the single crystal semiconductor layer 124 of the SOI substrate. In such a case, an element formed using the single crystal semiconductor layer 124 may be defective. Therefore, by providing an inspection process and finding in advance a substrate that cannot be used as a bond substrate, it is possible to reduce device defects and improve yield even when the multilayer substrate 200 is repeatedly used. In addition, providing an inspection step for improving yield is also effective from the viewpoint of increasing the use efficiency of the single crystal semiconductor substrate.

In the inspection process, the state of the multilayer substrate 200 is inspected. For example, the thickness and warpage amount of the multilayer substrate 200 are measured. In particular, it is preferable to measure the thickness of the single crystal semiconductor substrate 100 (thickness up to the bonding interface). In addition, it is preferable to observe the state (the presence or absence of scratches) of the surface of the multilayer substrate 200 (the surface of the single crystal semiconductor substrate 100). This is because as the single crystal semiconductor substrate 100 becomes thinner and closer to the vicinity of the bonding interface, there is a high possibility that defects or the like exist. The thickness and the amount of warpage of the laminated substrate 200 can be measured using a laser displacement meter. Moreover, observation of the surface state (the presence or absence of a flaw) etc. of the laminated substrate 200 can be performed using a microscope.

After performing such an inspection, it is possible to determine whether or not to reuse the laminated substrate 200 as a bond substrate in accordance with the result of the inspection process. For example, in the inspection process, the multilayer substrate 200 that satisfies a predetermined condition is reused as a bond substrate in an SOI substrate manufacturing process. On the other hand, for the stacked substrate 200 that does not satisfy the predetermined condition, the single crystal semiconductor substrate 100 and the insulating layer 142 are removed by polishing or the like to expose the surface of the single crystal semiconductor substrate 150 (FIG. 6E-E 3)), the single crystal semiconductor substrate 150 can be used as a bond substrate in an SOI manufacturing process (see FIGS. 1 and 3).

Whether or not the multilayer substrate 200 satisfies the predetermined condition can be determined according to the thickness of the single crystal semiconductor substrate 100 constituting the multilayer substrate 200, for example. In addition to the thickness of the single crystal semiconductor substrate 100, it can be determined as appropriate according to the amount of warpage and the surface state.

Note that the inspection process may be provided before the planarization process.

By providing the inspection process, even when a defect exists in the stacked substrate 200, the formation of the defect in the single crystal semiconductor layer 124 of the SOI substrate can be reduced. As a result, it is possible to suppress a defect from occurring in an element formed using the single crystal semiconductor layer 124.

Note that the structure described in this embodiment can be combined as appropriate with any of the structures described in the other embodiments in this specification.

(Embodiment 4)
In this embodiment, a method for bonding a single crystal semiconductor substrate used as a bond substrate and a base substrate in a manufacturing process of an SOI substrate will be described in detail with reference to drawings. Specifically, in the said embodiment, it respond | corresponds to FIG. 1 (A)-(D), FIG. 3 (A)-(D), and FIG. 7 (A)-(D).

First, the single crystal semiconductor substrate 100 is prepared (see FIG. 8A-1). The surface of the single crystal semiconductor substrate 100 may be cleaned in advance using sulfuric acid / hydrogen peroxide (SPM), ammonia / hydrogen peroxide (APM), hydrochloric acid / hydrogen peroxide (HPM), dilute hydrofluoric acid (DHF), etc. To preferred. Further, cleaning may be performed by alternately discharging dilute hydrofluoric acid and ozone water.

Next, an oxide film 132 is formed on the surface of the single crystal semiconductor substrate 100 (see FIG. 8A-2).

As the oxide film 132, for example, a single layer such as a silicon oxide film or a silicon oxynitride film, or a film in which these layers are stacked can be used. These films can be formed using a thermal oxidation method, a CVD method, a sputtering method, or the like. In the case where the oxide film 132 is formed by a CVD method, a silicon oxide film formed using an organic silane such as tetraethoxysilane (abbreviation: TEOS: chemical formula Si (OC ₂ H ₅ ) ₄ ) is oxidized. Use in the membrane 132 is preferable from the viewpoint of productivity.

In this embodiment, the single crystal semiconductor substrate 100 is subjected to thermal oxidation treatment to form an oxide film 132 (here, a SiOx film) (see FIG. 8A-2). The thermal oxidation treatment is preferably performed by adding halogen in an oxidizing atmosphere.

For example, the single crystal semiconductor substrate 100 is subjected to thermal oxidation treatment in an oxidizing atmosphere to which chlorine (Cl) is added, so that the oxide film 132 subjected to chlorine oxidation is formed. In this case, the oxide film 132 is a film containing chlorine atoms.

Chlorine atoms contained in the oxide film 132 form strain. As a result, the moisture absorption ratio of the oxide film 132 is improved and the diffusion rate is increased. That is, when moisture is present on the surface of the oxide film 132, moisture present on the surface can be quickly absorbed and diffused into the oxide film 132.

As an example of the thermal oxidation treatment, a temperature of 900 ° C. to 1150 ° C. (typical) in an oxidizing atmosphere containing hydrogen chloride (HCl) at a ratio of 0.5 to 10% by volume (preferably 3% by volume) with respect to oxygen. Specifically, it can be carried out at 1000 ° C.). The treatment time may be 0.1 to 6 hours, preferably 0.5 to 1 hour. The thickness of the oxide film to be formed is 10 nm to 1000 nm (preferably 50 nm to 300 nm), for example, 100 nm.

In this embodiment, the concentration of chlorine atoms contained in the oxide film 132 is controlled to be 1 × 10 ¹⁷ atoms / cm ³ to 1 × 10 ²¹ atoms / cm ³ . By containing chlorine atoms in the oxide film 132, the effect of preventing heavy metals (eg, Fe, Cr, Ni, Mo, etc.) that are extrinsic impurities from being collected and the single crystal semiconductor substrate 100 from being contaminated is obtained. Play.

When the oxide film 132 contains halogen such as chlorine by HCl oxidation or the like, impurities (for example, movable ions such as Na) that adversely affect the single crystal semiconductor substrate can be gettered. In other words, by heat treatment performed after the oxide film 132 is formed, impurities contained in the single crystal semiconductor substrate are deposited on the oxide film 132 and are captured by reacting with halogen (eg, chlorine). Accordingly, the impurity collected in the oxide film 132 can be fixed and contamination of the single crystal semiconductor substrate 100 can be prevented. Further, the oxide film 132 can function as a film for fixing impurities such as Na contained in the glass when bonded to a glass substrate.

In particular, the inclusion of halogen such as chlorine in the film as the oxide film 132 by HCl oxidation or the like is effective in the case of insufficient cleaning of the semiconductor substrate or for the contamination removal of the semiconductor substrate used repeatedly. It becomes.

Further, the halogen atoms contained in the oxide film 132 are not limited to chlorine atoms. The oxide film 132 may contain fluorine atoms. In order to fluorinate the surface of the single crystal semiconductor substrate 100, the surface of the single crystal semiconductor substrate 100 is immersed in hydrofluoric acid and then thermally oxidized in an oxidizing atmosphere, or NF ₃ is added to the oxidizing atmosphere and heat is applied. An oxidation treatment may be performed.

Next, by irradiating the single crystal semiconductor substrate 100 with ions having kinetic energy, an embrittled region 104 having a damaged crystal structure is formed at a predetermined depth of the single crystal semiconductor substrate 100 (FIG. 8A-A). 3)). As shown in FIG. 4A-3, a region having a predetermined depth from the surface of the single crystal semiconductor substrate 100 is obtained by irradiating the single crystal semiconductor substrate 100 with the accelerated ions 103 through the oxide film 132. The ions 103 can be added to the fragile regions 104 to be formed. The ions 103 are ions that are excited by generating a plasma of the source gas by exciting the source gas and extracting ions contained in the plasma from the plasma by the action of an electric field.

The depth of the region where the embrittlement region 104 is formed can be adjusted by the kinetic energy, mass and charge of the ions 103, and the incident angle of the ions 103. Kinetic energy can be adjusted by acceleration voltage, dose, etc. An embrittled region 104 is formed in a region having a depth substantially equal to the average penetration depth of the ions 103. Therefore, the thickness of the single crystal semiconductor layer separated from the single crystal semiconductor substrate 100 is determined by the depth to which the ions 103 are added. The depth at which the embrittlement region 104 is formed is adjusted so that the thickness of the single crystal semiconductor layer is 10 nm to 500 nm, preferably 50 nm to 200 nm.

The embrittlement region 104 can be formed by ion doping treatment. The ion doping process can be performed using an ion doping apparatus. A typical ion doping apparatus is a non-mass separation type apparatus that irradiates an object to be processed disposed in a chamber with all ion species generated by plasma excitation of a process gas. The non-mass separation type apparatus is because the object to be processed is irradiated with all ion species without mass separation of ion species in the plasma. On the other hand, the ion implantation apparatus is a mass separation type apparatus. An ion implantation apparatus is an apparatus that mass-separates ion species in plasma and irradiates a target object with ion species having a specific mass.

The main components of the ion doping apparatus are a chamber in which an object to be processed is arranged, an ion source for generating desired ions, and an acceleration mechanism for accelerating and irradiating ions. The ion source includes a gas supply device that supplies a source gas for generating a desired ion species, an electrode for generating a plasma by exciting the source gas, and the like. As an electrode for forming plasma, a filament-type electrode, an electrode for capacitively coupled high-frequency discharge, or the like is used. The acceleration mechanism includes an electrode such as an extraction electrode, an acceleration electrode, a deceleration electrode, and a ground electrode, and a power source for supplying power to these electrodes. The electrode constituting the acceleration mechanism is provided with a plurality of openings and slits, and ions generated by the ion source are accelerated through the openings and slits provided in the electrodes. Note that the configuration of the ion doping apparatus is not limited to that described above, and a mechanism according to need is provided.

In this embodiment, hydrogen is added to the single crystal semiconductor substrate 100 with an ion doping apparatus. A gas containing hydrogen is supplied as a plasma source gas. For example, H ₂ is supplied. Hydrogen gas is excited to generate plasma, and ions contained in the plasma are accelerated without mass separation, and the single crystal semiconductor substrate 100 is irradiated with the accelerated ions.

In the ion doping apparatus, the ratio of H ₃ ^{+ to} the total amount of ion species (H ⁺ , H ₂ ⁺ , H ₃ ⁺ ) generated from hydrogen gas is 50% or more. More preferably, the ratio of H ₃ ⁺ is 80% or more. Since the ion doping apparatus does not perform mass separation, one (H ₃ ⁺ ) of a plurality of ion species generated in plasma is preferably 50% or more, and more preferably 80% or more. By irradiation with ions having the same mass, ions can be added while being concentrated at the same depth in the single crystal semiconductor substrate 100.

In order to form the embrittled region 104 in a shallow region, the acceleration voltage of the ions 103 needs to be lowered. However, by increasing the proportion of H ₃ ⁺ ions in the plasma, hydrogen ions can be efficiently converted into a single crystal. It can be added to the semiconductor substrate 100. Since H ₃ ⁺ ions have a mass three times that of H ⁺ ions, when one hydrogen atom is added at the same depth, the acceleration voltage of H ₃ ⁺ ions is three times the acceleration voltage of H ⁺ ions. It becomes possible to do. If the acceleration voltage of ions can be increased, the tact time of the ion irradiation process can be shortened, and productivity and throughput can be improved.

Since the ion doping apparatus is inexpensive and excellent in large area processing, irradiation with H ₃ ⁺ using such an ion doping apparatus improves the semiconductor characteristics, increases the area, reduces the cost, and improves the productivity. A remarkable effect such as can be obtained. In addition, when an ion doping apparatus is used, heavy metal may be introduced at the same time. However, by irradiating ions through the oxide film 132 containing chlorine atoms, contamination of the single crystal semiconductor substrate 100 with heavy metal is prevented. Can be prevented.

Note that the step of irradiating the single crystal semiconductor substrate 100 with the accelerated ions 103 can be performed with an ion implantation apparatus. The ion implantation apparatus is a mass separation type apparatus that mass-separates a plurality of ion species generated by plasma-exciting a source gas from a target object disposed in a chamber and irradiates specific ion species. Therefore, when an ion implantation apparatus is used, H ⁺ ions and H ₂ ⁺ ions generated by exciting hydrogen gas or PH ₃ are mass-separated to accelerate one of the H ⁺ ions or the H ₂ ⁺ ions. Then, the single crystal semiconductor substrate 100 is irradiated.

Next, the base substrate 120 is prepared (see FIG. 8B-1).

In using the base substrate 120, it is preferable to clean the surface of the base substrate 120 in advance. Specifically, the base substrate 120 is subjected to ultrasonic cleaning using hydrochloric acid / hydrogen peroxide (HPM), sulfuric acid / hydrogen peroxide (SPM), ammonia / hydrogen peroxide (APM), dilute hydrofluoric acid (DHF), or the like. For example, it is preferable to ultrasonically clean the surface of the base substrate 120 using hydrochloric acid / hydrogen peroxide. By performing such a cleaning process, the surface of the base substrate 120 can be planarized and the remaining abrasive particles can be removed.

Next, a nitrogen-containing layer 121 (eg, an insulating film containing nitrogen such as a silicon nitride film or a silicon nitride oxide film) is formed over the surface of the base substrate 120 (see FIG. 8B-2).

In this embodiment, the nitrogen-containing layer 121 is a layer (a bonding layer) that is bonded to the oxide film 132 provided over the single crystal semiconductor substrate 100. In addition, the nitrogen-containing layer 121 is formed such that when a single crystal semiconductor layer having a single crystal structure is provided on the base substrate later, impurities such as Na (sodium) contained in the base substrate diffuse into the single crystal semiconductor layer. Functions as a barrier layer to prevent.

In addition, since the nitrogen-containing layer 121 is used as a bonding layer, it is preferable to smooth the surface of the nitrogen-containing layer 121 in order to suppress poor bonding. Specifically, the average surface roughness (Ra) of the surface of the nitrogen-containing layer 121 is 0.5 nm or less, the root mean square roughness (Rms) is 0.60 nm or less, and more preferably, the average surface roughness is 0.35 nm. Thereafter, the nitrogen-containing layer 121 is formed so that the root mean square roughness is 0.45 nm or less. The film thickness is 10 nm to 200 nm, preferably 50 nm to 100 nm.

Next, the surface of the single crystal semiconductor substrate 100 and the surface of the base substrate 120 are opposed to each other, and the surface of the oxide film 132 and the surface of the nitrogen-containing layer 121 are bonded (see FIG. 8C).

Here, after the single crystal semiconductor substrate 100 and the base substrate 120 are brought into close contact with each other through the oxide film 132 and the nitrogen-containing layer 121, 1 to 500 N / cm ² , preferably 1 to 20 N is provided at one position of the single crystal semiconductor substrate 100. A pressure of about / cm ² is applied. The oxide film 132 and the nitrogen-containing layer 121 start to be joined from the portion where the pressure is applied, and the junction is spontaneously formed and extends over the entire surface. This bonding process is performed at room temperature without van der Waals force or hydrogen bond, and is not accompanied by heat treatment. Therefore, a substrate having a low heat resistance temperature such as a glass substrate should be used for the base substrate 120. Can do.

Note that the surface treatment of the oxide film 132 formed over the single crystal semiconductor substrate 100 and the nitrogen-containing layer 121 formed over the base substrate 120 is performed before the single crystal semiconductor substrate 100 and the base substrate 120 are bonded to each other. It is preferable to carry out.

As the surface treatment, plasma treatment, ozone treatment, megasonic cleaning, two-fluid cleaning (a method of spraying functional water such as pure water or hydrogenated water together with a carrier gas such as nitrogen) or a combination of these methods can be performed. . In particular, after plasma treatment is performed on at least one surface of the oxide film 132 and the nitrogen-containing layer 121, an organic material on the surface of the oxide film 132 and the nitrogen-containing layer 121 is obtained by performing ozone treatment, megasonic cleaning, two-fluid cleaning, or the like. Etc. can be removed, and the surface can be made hydrophilic. As a result, the bonding strength between the oxide film 132 and the nitrogen-containing layer 121 can be improved.

Further, after the oxide film 132 and the nitrogen-containing layer 121 are bonded, it is preferable to perform a heat treatment for increasing the bonding strength. The temperature of this heat treatment is set to a temperature that does not cause cracks in the embrittled region 104, and for example, the heat treatment is performed in a temperature range of room temperature to less than 400 ° C. Further, the oxide film 132 and the nitrogen-containing layer 121 may be bonded while heating in this temperature range. For the heat treatment, a heating furnace such as a diffusion furnace or a resistance heating furnace, an RTA (Rapid Thermal Annealing) apparatus, a microwave heating apparatus, or the like can be used.

In general, when heat treatment is performed at the same time as or after bonding the oxide film 132 and the nitrogen-containing layer 121, a dehydration reaction proceeds at the bonding interface, the bonding interfaces approach each other, and hydrogen bonds are strengthened or covalent bonds are formed. As a result, the bonding is strengthened. In order to promote the dehydration reaction, it is necessary to remove moisture generated at the bonding interface by the dehydration reaction by performing a heat treatment at a high temperature. In other words, when the heat treatment temperature after bonding is low, moisture generated at the bonding interface due to the dehydration reaction cannot be effectively removed, so that the dehydration reaction does not proceed and it is difficult to sufficiently improve the bonding strength.

On the other hand, when an oxide film containing chlorine atoms or the like is used as the oxide film 132, the oxide film 132 can absorb and diffuse moisture, and thus heat treatment after bonding is performed at a low temperature. However, the moisture generated at the bonding interface by the dehydration reaction can be absorbed and diffused into the oxide film 132 to efficiently promote the dehydration reaction. In this case, even when a substrate having low heat resistance such as glass is used as the base substrate 120, the bonding strength between the oxide film 132 and the nitrogen-containing layer 121 can be sufficiently improved. Further, by performing a plasma treatment by applying a bias voltage, micropores are formed in the vicinity of the surface of the oxide film 132, and moisture is effectively absorbed and diffused. Even at low temperatures, the oxide film 132 and the nitrogen-containing layer are formed. The bonding strength of 121 can be improved.

Next, heat treatment is performed and separation is performed in the embrittlement region 104, whereby the single crystal semiconductor layer 124 is provided over the base substrate 120 with the oxide film 132 and the nitrogen-containing layer 121 interposed therebetween (see FIG. 8D).

By performing the heat treatment, the added element is precipitated in the minute holes formed in the embrittled region 104 due to the temperature rise, and the internal pressure rises. The increase in pressure causes a change in volume in a minute hole in the embrittled region 104 and a crack occurs in the embrittled region 104, so that the single crystal semiconductor substrate 100 is cleaved along the embrittled region 104. Since the oxide film 132 is bonded to the base substrate 120, the single crystal semiconductor layer 124 separated from the single crystal semiconductor substrate 100 is formed over the base substrate 120. In addition, the temperature of the heat treatment here is a temperature that does not exceed the strain point of the base substrate 120.

For this heat treatment, a heating furnace such as a diffusion furnace or a resistance heating furnace, a rapid thermal annealing (RTA) apparatus, a microwave heating apparatus, or the like can be used. For example, when an RTA apparatus is used, the heating can be performed at a heating temperature of 550 ° C. or more and 730 ° C. or less and a treatment time of 0.5 minutes or more and 60 minutes or less.

Note that the heat treatment for increasing the bonding strength between the base substrate 120 and the oxide film 132 described above is not performed, and the bonding strength between the oxide film 132 and the nitrogen-containing layer 121 is increased by performing the heat treatment in FIG. The increase heat treatment step and the separation heat treatment step in the embrittled region 104 may be performed simultaneously.

Through the above steps, an SOI substrate in which the single crystal semiconductor layer 124 is provided over the base substrate 120 with the oxide film 132 and the nitrogen-containing layer 121 interposed therebetween can be manufactured.

By using the method in this embodiment, even when the nitrogen-containing layer 121 is used as a bonding layer, the bonding strength between the base substrate 120 and the single crystal semiconductor layer 124 can be improved and the reliability can be improved. Can do. As a result, diffusion of impurities to the single crystal semiconductor layer 124 formed over the base substrate 120 can be suppressed, and an SOI substrate in which the base substrate 120 and the single crystal semiconductor layer 124 are firmly adhered can be formed.

In addition, by providing a nitrogen-containing layer on the base substrate side and forming an oxide film containing halogen such as chlorine on the semiconductor substrate side, the manufacturing process is simplified and impurities are added to the semiconductor substrate before bonding to the base substrate. Intrusion of elements can be suppressed. In addition, by forming an oxide film containing halogen such as chlorine as a bonding layer provided on the semiconductor substrate side, even when heat treatment after bonding is performed at a low temperature, the dehydration reaction is efficiently promoted to increase the bonding strength. Can be improved.

After that, the separated single crystal semiconductor substrate 100 can be reused in the manufacturing process of the SOI substrate as described in Embodiment Mode 1.

Note that although the case where the oxide film 132 is formed over the single crystal semiconductor substrate 100 and the nitrogen-containing layer 121 is formed over the base substrate 120 is described in this embodiment mode, the present invention is not limited thereto. For example, the oxide film 132 and the nitrogen-containing layer may be sequentially stacked over the single crystal semiconductor substrate 100, and the surface of the nitrogen-containing layer formed over the oxide film 132 and the surface of the base substrate 120 may be bonded. Good. In this case, the nitrogen-containing layer may be provided before or after the embrittlement region 104 is formed. Note that an oxide film (eg, silicon oxide) may be formed over the nitrogen-containing layer, and the surface of the oxide film and the surface of the base substrate 120 may be bonded to each other.

In addition, in the case where mixing of impurities from the base substrate 120 to the single crystal semiconductor layer 124 does not cause a problem, the oxide film provided over the single crystal semiconductor substrate 100 without providing the nitrogen-containing layer 121 over the base substrate 120. The surface 132 may be bonded to the surface of the base substrate 120. In this case, the step of providing the nitrogen-containing layer can be omitted.

Note that the structure described in this embodiment can be combined as appropriate with any of the structures described in the other embodiments in this specification.

4A and 4B illustrate an example of a method for manufacturing an SOI substrate of the present invention. 4A and 4B illustrate an example of a method for manufacturing an SOI substrate of the present invention. 4A and 4B illustrate an example of a method for manufacturing an SOI substrate of the present invention. 10A and 10B illustrate an example of a method for bonding single crystal semiconductor substrates to each other in a method for manufacturing an SOI substrate of the present invention. 10A and 10B illustrate an example of a method for bonding single crystal semiconductor substrates to each other in a method for manufacturing an SOI substrate of the present invention. 10A and 10B illustrate an example of a method for bonding single crystal semiconductor substrates to each other in a method for manufacturing an SOI substrate of the present invention. 4A and 4B illustrate an example of a method for manufacturing an SOI substrate of the present invention. 9A and 9B illustrate an example of a method for bonding a bond substrate and a base substrate in a method for manufacturing an SOI substrate of the present invention. 10A and 10B illustrate an example of a method for bonding single crystal semiconductor substrates to each other in a method for manufacturing an SOI substrate of the present invention. 4A and 4B illustrate a surface, a chamfered portion, and an end surface of a single crystal semiconductor substrate in a method for manufacturing an SOI substrate of the present invention.

Explanation of symbols

100 Single crystal semiconductor substrate 101 Surface 102 Insulating layer 103 Ion 104 Embrittlement region 110 Single crystal semiconductor substrate 111 Front surface 112 Back surface 113 End surface 120 Base substrate 121 Nitrogen-containing layer 124 Single crystal semiconductor layer 132 Oxide film 142 Insulating layer 144 Insulating layer 146 Insulating Layer 150 Single crystal semiconductor substrate 151 Surface 152 Back surface 153 End surface 200 Multilayer substrate 201 Surface 203 End surface 211 Inclined surface 212 Inclined surface 213 Inclined surface 111a Main surface 111b Surface side chamfered portion 112a Main surface 112b Back surface side chamfered portion 151a Main surface 151b Surface side surface Chamfer 152a Main surface 152b Back side chamfer 201a Main surface 202a Main surface 201b Front side chamfer 202b Back side chamfer

Claims (8)

Irradiating ions to the surface of the first single crystal semiconductor substrate that has a front side chamfered portion, a back side chamfered portion, and an end face that connects the front side chamfered portion and the back side chamfered portion to form a bond substrate A first step of forming an embrittled region in the first single crystal semiconductor substrate and bonding the first single crystal semiconductor substrate and the base substrate through an insulating layer;
A second step of separating the first single crystal semiconductor substrate in the embrittlement region and forming a single crystal semiconductor layer on the base substrate via the insulating layer;
A third step of performing a planarization process on the first single crystal semiconductor substrate separated in the embrittlement region in the second step,
The first single crystal semiconductor substrate that has been subjected to the planarization treatment is again used as the bond substrate a plurality of times, and the first to third steps are repeated,
When the surface side chamfered portion of the first single crystal semiconductor substrate is eliminated in the third step, the first single crystal semiconductor substrate is bonded to the second single crystal semiconductor substrate to form a stacked substrate. ,
A method for manufacturing an SOI substrate, comprising: providing a front side chamfered portion and a back side chamfered portion on the laminated substrate; and using the laminated substrate as a bond substrate in the first step. A front side chamfer, a back side chamfer, and an end face connecting the front side chamfer and the back side chamfer, and irradiating the surface of the first single crystal semiconductor substrate serving as a bond substrate with ions Forming a brittle region in the first single crystal semiconductor substrate, and bonding the first single crystal semiconductor substrate and the base substrate through an insulating layer;
A second step of separating the first single crystal semiconductor substrate in the embrittlement region and forming a single crystal semiconductor layer on the base substrate via the insulating layer;
A third step of performing a planarization process on the first single crystal semiconductor substrate separated in the embrittlement region in the second step,
The first single crystal semiconductor substrate that has been subjected to the planarization treatment is used again and again as the bond substrate, and the first to third steps are repeatedly performed.
A laminated substrate is formed by bonding the first single crystal semiconductor substrate to the second single crystal semiconductor substrate in a state in which the surface side chamfered portion of the first single crystal semiconductor substrate that has been repeatedly used remains. ,
A method for manufacturing an SOI substrate, comprising: providing a front side chamfered portion and a back side chamfered portion on the laminated substrate; and using the laminated substrate as a bond substrate in the first step. In claim 1 or claim 2,
The surface chamfered portion of the multilayer substrate is formed on the first inclined surface formed on the first single crystal semiconductor substrate and on the same surface as the first inclined surface formed on the second single crystal semiconductor substrate. Provided by the second inclined surface provided on the top;
A method for manufacturing an SOI substrate, wherein an end face connecting the front side chamfered portion and the back side chamfered portion of the multilayer substrate is provided in the second single crystal semiconductor substrate. In any one of Claims 1 thru | or 3,
In the third step, an SOI substrate manufacturing method is provided, which includes an inspection step of inspecting a state of a surface chamfered portion of the first single crystal semiconductor substrate after the planarization treatment. In any one of Claims 1 thru | or 4,
Bonding the first single crystal semiconductor substrate and the second single crystal semiconductor substrate,
After performing surface treatment on at least one of the surface of the first single crystal semiconductor substrate and the surface of the second single crystal semiconductor substrate, the surface of the first single crystal semiconductor substrate and the second single crystal semiconductor A method for manufacturing an SOI substrate, which is performed by directly bonding the surfaces of the substrate. In claim 5,
The surface treatment is performed by irradiating argon in a vacuum to activate at least one of the surface of the first single crystal semiconductor substrate and the surface of the second single crystal semiconductor substrate. Method. In any one of Claims 1 thru | or 4,
The bonding of the first single crystal semiconductor substrate and the second single crystal semiconductor substrate is performed through a bonding layer formed on at least one of the first single crystal semiconductor substrate or the second single crystal semiconductor substrate. A method for manufacturing an SOI substrate. In any one of Claims 1 thru | or 7,
A method for manufacturing an SOI substrate, wherein a glass substrate, a single crystal semiconductor substrate, or a polycrystalline semiconductor substrate is used as the base substrate.

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