JP5950269B2 - Substrate processing method and substrate - Google Patents

Description

  The present invention relates to a substrate processing method for processing a silicon single crystal substrate, and a silicon single crystal substrate that is processed inside.

  Conventionally, when manufacturing a semiconductor wafer represented by a silicon (Si) wafer, a cylindrical ingot solidified from a silicon melt melted in a quartz crucible is cut into blocks of an appropriate length, The peripheral edge is ground to a target diameter, and then the block ingot is sliced into a wafer shape with a wire saw to manufacture a semiconductor wafer (see, for example, Patent Documents 1 and 2).

  The semiconductor wafer manufactured in this way is subjected to various processes such as circuit pattern formation in the previous process in order and used in the subsequent process. In this subsequent process, the back surface is back-grinded and thinned. Accordingly, the thickness is adjusted to about 750 μm to 100 μm or less, for example, about 75 μm or 50 μm.

  A conventional semiconductor wafer is manufactured as described above, and an ingot is cut with a wire saw, and a cutting allowance larger than the thickness of the wire saw is required for cutting, so a thin semiconductor wafer with a thickness of 0.1 mm or less It is very difficult to manufacture the product, and the product rate is not improved.

  On the other hand, the condensing point of the laser beam is aligned with the inside of the ingot with the condensing lens, and the ingot is relatively scanned with the laser beam to form a planar modified layer by multiphoton absorption inside the ingot. A substrate manufacturing method and a substrate manufacturing apparatus are disclosed in which a part of the ingot is peeled off using the modified layer as a peeling surface (see, for example, Patent Document 3 and Patent Document 4). In Patent Document 3, laser light is scanned concentrically or spirally, and in Patent Document 4, laser light is scanned in the XY directions using an XY stage.

  Also, two-component room-temperature curing adhesives are provided for temporary fixing when processing solar cells or slicing silicon ingots (for example, Patent Document 5 and Patent Document 6). Such an adhesive has a relatively weak adhesive strength so that it can be easily peeled and removed after temporarily fixing and processing a slice of a solar cell or ingot.

  Furthermore, a method has been proposed in which a wafer is manufactured by processing an inner surface with a laser beam while applying stress to the ingot, holding it with an adhesive, and peeling the wafer from the ingot (for example, see Patent Document 7).

On the other hand, it is known that there is a certain relationship between wavelength and transmittance in a silicon single crystal (see, for example, Non-Patent Document 1).
In this specification, a wafer is referred to as a substrate unless otherwise specified.

JP 2008-200772 A JP 2005-297156 A JP 2005-277136 A JP 2005-294325 A JP 2010-248395 A JP 2007-039532 A JP 2006-024782 A

E.D.Palik ed .: Handbook of Optical Constants of Solids, Academic Press, San Diego, (1985) 547

  An object of this invention is to provide the board | substrate processing method and board | substrate which provide a thin silicon substrate, ensuring a product rate.

  In order to solve the above-described problems, a substrate processing method for processing a single crystal silicon substrate according to the present invention includes a step of disposing a laser focusing unit on a substrate in a non-contact manner, and the laser focusing unit includes Irradiating the surface of the substrate with laser light, condensing the laser light inside the substrate, and relatively moving the laser condensing means and the substrate to form a modified layer inside the substrate; The modified layer has polycrystalline grains of polycrystalline silicon in a predetermined depth range from the surface of the substrate, and the modified layer is asymmetric in the depth direction of the substrate. It has a structure.

  The substrate according to the present invention is a silicon single crystal substrate whose inside is processed, and has a modified layer having polycrystalline grains of polycrystalline silicon in a predetermined depth range from the surface of the substrate, The modified layer has an asymmetric structure in the depth direction of the substrate.

  The irradiated laser beam preferably has a wavelength of 10% or more at a depth of 500 μm of the substrate.

  The irradiated laser light preferably has a pulse width of 50 ns or more.

The surface of the substrate is preferably a mirror finish .

  In the modified layer, the dimensions of the polycrystalline grains preferably have an asymmetric distribution in the depth direction of the substrate.

  In the modified layer, the size of the polycrystalline grains is preferably 150 μm or less.

It is a flowchart which shows a series of processes of a board | substrate processing method. It is a perspective view of a substrate internal processing apparatus. It is a top view of the stage which mounted the board | substrate. It is sectional drawing of the stage which mounted the board | substrate. It is a figure explaining irradiation of the laser beam with respect to a board | substrate. It is a figure which shows the wavelength dependence of the transmittance | permeability in a silicon single crystal. It is a figure explaining the asymmetrical structure of an internal modification layer. It is sectional drawing explaining the internal modification layer formed in the board | substrate. It is an infrared microscope image of an internal modified layer. It is sectional drawing explaining adhesion | attachment of the metal plate with respect to the single side | surface of a board | substrate. It is sectional drawing explaining adhesion | attachment of the metal plate with respect to both surfaces of a board | substrate. It is a front view which shows a cleaving apparatus. It is a photograph which shows the cut surface of a board | substrate. It is a figure which shows the frequency distribution of the roughness in the cross section of a board | substrate. It is a figure explaining peeling a board | substrate from a metal plate in water. 2 is a photograph of an internal modified layer of a substrate in Example 1. 4 is a cross-sectional photograph of a split surface in Example 2. It is a photograph of the internal modification layer of the substrate in a comparative example.

  Next, embodiments of the present invention will be described with reference to the drawings. In the following description of the drawings, the same or similar parts are denoted by the same or similar reference numerals. However, it should be noted that the drawings are schematic, and the relationship between the thickness and the planar dimensions, the ratio of the thickness of each layer, and the like are different from the actual ones. Therefore, specific thicknesses and dimensions should be determined in consideration of the following description. Moreover, it is a matter of course that portions having different dimensional relationships and ratios are included between the drawings.

  Further, the embodiments described below exemplify apparatuses and methods for embodying the technical idea of the present invention, and the embodiments of the present invention include the material, shape, structure, The layout is not specified as follows. Various modifications can be made to the embodiment of the present invention within the scope of the claims.

  As shown in FIG. 1, the substrate processing method of the present embodiment includes a substrate internal processing step (S11), a metal plate pretreatment step (S12), an adhesion / curing step (S13), and a cleaving step. It consists of a series of steps including (S14), an underwater peeling step (S15) and a drying step (S16). Below, these each process is demonstrated in order.

(Internal processing of substrate)
In the first step S11, the substrate is internally processed. This step is performed by the substrate internal processing apparatus 1. In the present embodiment, a silicon single crystal substrate 10 is used as the substrate 10 processed by the substrate internal processing apparatus 1.

  FIG. 2 is a perspective view showing the configuration of the substrate internal processing apparatus 100. The substrate internal processing apparatus 1 includes a stage 110, a stage support unit 120 that supports the stage 110 so as to be movable in the XY directions, and a substrate fixture 130 that is disposed on the stage 110 and fixes the substrate 10. ing.

  Further, the substrate internal processing apparatus 100 includes a laser light source 160, a condensing lens 170, and an aberration adjusting plate 180. The laser light 190 emitted from the laser light source 160 is passed through the condensing lens 160 and the aberration adjusting plate 180. Then, the substrate 10 is irradiated.

  FIG. 3 is a top view showing the substrate 10 placed on the stage 110. FIG. 4 is a cross-sectional view showing the substrate 10 placed on the stage 110.

  The substrate 10 is held on the stage 110 by the substrate fixture 130. The substrate fixture 130 fixes the substrate 10 by a fixing table 125 provided thereon. A normal adhesive layer, mechanical chuck, electrostatic chuck or the like can be applied to the fixed table 125.

  A condensing point P of the laser beam 190 that is condensed and irradiated on the substrate 10 forms a locus 12 having a predetermined shape in a region at a predetermined depth from the surface within the substrate 10. In addition, a two-dimensional internal reforming layer 14 can be formed.

  FIG. 5 is a diagram for explaining the formation of the internal modified layer 14 in the substrate 10.

  As shown in FIG. 5A, an aberration adjusting plate 180 having a predetermined refractive index may be disposed between the condenser lens 170 and the substrate 10 in order to adjust the aberration of the laser light 190. By arranging such an aberration adjusting plate 180, the laser light 190 incident on the substrate 10 has the depth direction and the width of the focal point P formed inside the substrate 10. Also by this, the internal modified layer 14 formed inside the substrate 10 can be formed to have a predetermined thickness t.

  FIG. 5B is a diagram illustrating the aberration caused by the aberration adjusting plate 170. Increasing the refractive index or thickness of the aberration adjusting plate 180 increases the aberration, and the separation between the condensing point P1 of the inner shaft component 190a and the condensing point P2 of the outer shaft component 190b becomes significant. By utilizing such properties, the structure of the internal reforming layer 14 can be controlled.

  FIG. 6 is a diagram showing the wavelength dependence of light transmittance in a silicon single crystal.

  The relationship shown in FIG. 6 is described in Non-Patent Document 1. The laser light source 160 of the substrate internal processing apparatus 100 according to the present embodiment has a wavelength of 10% or more at a depth of 500 μm from the surface of the silicon single crystal substrate 10. The pulse width of the laser light is 50 ns or more.

(Asymmetric internal reforming layer)
In the present embodiment, the internal modified layer 14 formed on the substrate 10 has an asymmetric structure in the depth direction of the substrate 10.

In a silicon single crystal, it is known that the transmittance varies depending on the substrate thickness even at the same wavelength, and the transmittance decreases as the substrate thickness increases. (For example, see Non-Patent Document 1.)
Also from this, an asymmetric structure can be formed as follows, for example. In other words, the upper layer becomes a higher energy processing condition than the internal modified layer 14 due to the difference in energy density of the processed portion in the thickness direction of the irradiated laser beam 190 with respect to the substrate 10.

  On the other hand, the lower layer of the internal reforming layer 14 has a larger energy loss for reaching the upper layer, resulting in lower energy processing conditions. Thereby, an asymmetric structure is formed in the cross section of the substrate 10.

  FIG. 7 is a diagram illustrating an asymmetric structure of the internal reforming layer 14. In addition, the code | symbol in a figure is the same as that of FIG. 8 mentioned later.

  FIG. 7 shows a cross-sectional transmission photograph of the sample irradiated with high-energy beam and Raman spectroscopic measurement data in the cross-section L so that cracks are formed in the substrate 10 other than the processing marks constituting the internal modified layer 14. ing. The Raman spectroscopic measurement measures an area where there is no crack A other than the processing mark in the drawing.

  This shows that the compressive stress strain is more strongly applied to the upper part of the processing mark even though the processing mark is formed in the central part in the thickness direction of the substrate 10.

  The internal modified layer 14 is made of polycrystalline silicon formed by condensing and irradiating the laser beam 190 on the substrate 10 to change the bonding state by being cooled after the silicon single crystal is melted. It has polycrystalline grains.

  The size of the polycrystalline grains, that is, the grain size can be adjusted by controlling the energy density, the number of times of irradiation, the irradiation method, and the like regarding the laser beam 190 to be irradiated. However, since the size of the polycrystalline grains greatly affects the surface roughness of the cleaved substrate 10, the polycrystalline grains are preferably 150 μm or less, and more preferably 30 μm or less.

  The dimensions and the number of polycrystalline grains can be confirmed by nondestructive inspection using an infrared microscope during or after processing of the substrate 10. Specifically, the substrate 10 is observed with transmitted light from the irradiation direction of the laser light 190 with an infrared microscope, and the region having a lower transmittance than the single crystal portion is made polycrystalline, so that the transmittance of the internal modified layer 14 is low. The size and the degree of formation of the polycrystalline grains can be determined from the distribution.

  The internal modified layer 14 is preferably exposed at the end of the substrate 10 in order to improve the yield in the cleaving process described later. As a method for exposing the internal modified layer 14, the cleavage of crystal orientation may be used, or the laser beam 190 may be used.

  Here, when the internal modified layer 14 is formed by irradiating the substrate 10 with the laser beam 190, the substrate 10 is cooled and maintained in a predetermined temperature range. Such a cooling method may be natural cooling or cooling by spraying a fluid. The cooling direction may be from the lower part of the substrate fixture 130 for fixing the substrate 10 or from the upper part of the substrate 10.

  Specifically, a fiber ns 20 manufactured by JenLas is used as the laser light source 160, an output of 0.57 W, a pulse width of 200 ns, a repetition frequency of 50 kHz, a scanning speed of 50 mm / s, a DF (depth of focus) of 100 μm, and an infrared objective lens with Si aberration correction. A sample was manufactured by processing the substrate 10 under the condition of 100 times (DF 100 μm).

  FIG. 8 is a view showing a cross-sectional transmission photograph of the internal modified layer 14 formed on the substrate 10 and Raman spectroscopic measurement data in the cross-section.

  In the transmission photograph on the left side in FIG. 8, the internal modified layer 14 having a thickness t is formed in a predetermined range in the depth direction of the substrate 10, and the light transmittance decreases in the internal modified layer 14 due to the presence of polycrystalline grains. You can see that

  The right side in FIG. 8 is obtained by measuring backward Raman scattering in the cross section L of the substrate 10. In the figure, the measurement point a indicates the wave number, and the measurement point b indicates the half width.

  According to this measurement result, it is suggested that both the wave number and the half value width are maximized in the vicinity of the internal modified layer 14, and the stress in the substrate 10 is also maximized in the vicinity of the internal modified layer 14.

  Here, the region near the inner modified layer 14 means a boundary region between the inner modified layer 14 and the single crystal layer in which polycrystalline grains are formed by irradiation with the laser beam 190. In the region near the internal reforming layer 14, a large amount of stress is accumulated because the single crystal and the single crystal formed by quenching the melted single crystal are discontinuously adjacent to each other. Such dimensions and properties of the region near the internal modified layer 14 can be controlled by laser processing conditions.

  For example, it is possible to control the cohesive force of polycrystalline grains in the region near the inner modified layer 14. By controlling the agglomeration force of the polycrystalline grains, the substrate 10 can be divided by applying a predetermined force in the region near the inner modified layer 14.

  FIG. 9 is a cross-sectional photograph showing polycrystalline grains in the internal modified layer 14. (A), (b), and (c) in FIG. 9 are parallel to the surface of the substrate from the upper surface to the lower surface of the internal modified layer 14, that is, at different positions in the direction of increasing depth from the surface of the substrate 10. It is a photograph of a simple cross section. (D) is an enlarged view of part of (a).

  According to these cross-sectional photographs, the polycrystalline grains are formed along the laser scanning direction, but the size and density of the polycrystalline grains vary depending on the depth in the substrate 10, and the internal modified layer 14 has a depth of the substrate 10. It can be seen that the structure is asymmetric in the direction.

  These photographs were taken by sequentially changing the depth of focus of the infrared microscope. For the photographing, a transmission image was used using an Olympus infrared microscope BX51-IR.

(Metal plate pretreatment)
In step S12, a metal plate for bonding and fixing the substrate 10 with an adhesive is pretreated. As this metal plate, a metal plate having a predetermined rigidity and having a predetermined thickness and dimensions suitable for bonding of the substrate 10 and subsequent processes can be used. As long as predetermined parallelism and flatness are obtained, the metal plate may be machined such as a punch hole for fixing the device.

  Since the metal plate undergoes an underwater peeling step in step S15 described later, it is preferable that the metal plate is passive in order to suppress substrate contamination, and a thin oxide film layer is formed for the purpose of reducing the takt time for underwater peeling. Is preferred.

  In step S12, the surface is degreased to facilitate underwater peeling, and the active oxide layer is exposed by removing the oxide film layer on the surface in order to ensure adhesion with the adhesive.

  There are mechanical and chemical methods for removing the oxide film layer. The chemical method specifically includes acid cleaning using chemicals and degreasing treatment. Specific examples of the mechanical method include sand blasting and shot blasting, but the method of damaging the surface of the metal plate with sand paper is the simplest, and the particle size is preferably # 80 to 2000, and the surface damage of the metal plate # 150 to 800 is more preferable.

(Adhesion / curing)
In step S13, the substrate 10 on which the internal modified layer 14 is formed in step S11 and the metal plate pretreated in step S12 are used, and the substrate 10 is bonded to the metal plate using an adhesive, and the adhesive is cured. Such an adhesive may be any adhesive that is stronger than the cohesive strength of the polycrystalline grains that form the region near the inner modified layer 14 of the substrate 10.

  FIG. 10 is a cross-sectional view illustrating a method for fixing one side of the substrate 10 to the metal plate 20 using an adhesive 25. In the figure, a substrate 10 is placed on a metal plate 20 to which an adhesive 25 is applied, and a push plate 33 supported by a spacer 31 is placed thereon.

  In the present embodiment, an adhesive 25 made of an acrylic two-component monomer component that cures using metal ions as a reaction initiator is used. In such an adhesive 25, the uncured monomer and the cured reaction product are insoluble in water, and do not contaminate when the cleaved substrate 10 is peeled off in water.

  The application thickness of the adhesive 25 is preferably 0.1 to 1 mm, and more preferably 0.15 to 0.35 mm before curing. When the coating thickness of the adhesive 25 is excessively large, a long time is required for complete curing, and cohesive failure of the adhesive 25 easily occurs when the substrate 10 is cleaved. When the coating thickness is small, it takes a long time to peel off the cleaved substrate 10 in water.

  The application thickness of the adhesive 25 is controlled by a method of fixing the metal plate 20 to be bonded to an arbitrary height, but can be simply performed using a spacer 31 such as a shim plate. When the parallelism between the metal plates 20 to be bonded cannot be obtained by only one sheet, the parallelism may be obtained by using one or more auxiliary spacers.

  When it is desired to strictly control the coating thickness, it is preferable to bond the other surface after curing on one surface. At this time, a resin film not containing metal ions may be used as the cover layer in order to prevent the adhesive 25 from being cured on the substrate 10 having the non-adhesive surface.

  When bonding one side of the substrate 10 at a time, the adhesive 25 may be the upper surface or the lower surface of the substrate 10. Further, the adhesive 25 is not necessarily applied to the entire surface of the substrate 10.

  FIG. 11 is a cross-sectional view illustrating a method of fixing both surfaces of the substrate 10 to the metal plate 20 using an adhesive.

  In this case, both the upper and lower surfaces of the substrate 10 are simultaneously bonded to the first metal plate 20 and the second metal plate 21 by the adhesive 25. The distance between the first metal plate 20 and the second metal plate 21 is set by a spacer 31 (not shown).

  In this way, the substrate 10 forms an integral structure 40 in which both surfaces are sandwiched and bonded by the first and second metal plates 20 and 21.

(Cleavage)
In step S14, the substrate 10 bonded to the metal plates 20 and 21 with the adhesive 25 in step S13 is cleaved.

  FIG. 12 is a front view showing a cleaving apparatus 50 for cleaving the substrate 10. In the cleaving apparatus 50, the structure 40 in which the first and second metal plates 20 and 21 are bonded to both surfaces of the substrate 10 is placed on the mount 52.

  For example, the structure 40 may be fixed to the gantry 52 using a through hole provided in the second metal plate 21. In this state, a downward pressing force is applied to the first metal plate 20 by the cleaving jig 54. As a result, the substrate 10 receives a reverse force in the direction of both the upper and lower surfaces bonded to the first and second metal plates 20 and 21. The drive source of the cleaving jig 54 may be a hydraulic type, a pneumatic type, or a hybrid type.

  When the force applied to the split jig 54 exceeds a predetermined threshold value, the substrate 10 is divided and the structure 40 is separated into upper and lower parts. In the present embodiment, since the internal modified layer 14 is formed asymmetrically in the depth direction of the substrate 10, the substrate 10 is cleaved in the region near the internal modified layer 14.

  FIG. 13 is a photograph showing a cut section of the cut substrate 10. FIG. 14 is a diagram illustrating an example of the roughness frequency distribution in the fractured surface.

  FIG. 14 is a diagram showing the distribution of roughness in the fractured surface. For the measurement, NH-3NT manufactured by Mitaka Kogyo Co., Ltd. was used as a non-contact three-dimensional measuring apparatus.

  In the present embodiment, the roughness frequency is mainly distributed in the range of 80 to 100 μm in the split section. Such roughness is particularly useful for suppressing reflection of incident light on the surface of the substrate 10 used in the solar cell.

(Underwater peeling)
In step S15, the board | substrate 10 is peeled from the metal plates 20 and 21 in water about the structure 40 divided | segmented in step S14.

  FIG. 15 is a diagram for explaining a method of peeling the substrate 10 from the metal plate 20 in water. In the present embodiment, the substrate 10 bonded to the metal plates 20 and 21 with the adhesive 25 is immersed in hot water of 80 to 100 ° C. stored in the water tank 60. After a predetermined time has elapsed, the adhesive reacts with water in a predetermined manner, and the adhesive force is lost from the adhesive 25. Therefore, the substrate 10 is separated from the metal plates 20, 21 by peeling the adhesive 25 from the substrate 10 in water. can do.

(Dry)
In step S16, the substrate 10 from which the adhesive 25 has been peeled in step S15 is dried.

  The substrate 10 may be dried by leaving it in an indoor environment, may be replaced with a clean water-soluble volatile solvent to promote drying, or may be dried by applying hot air.

  The water-soluble volatile solvent is an organic solvent having a hydroxyl group having a vapor pressure of 2 kPa or higher at 20 ° C., and specific examples include 2-propanol and methyl alcohol. Ethyl alcohol is preferable in consideration of the environment.

Example 1
A substrate 10 made of a single crystal silicon ingot having a 15 mm square and a thickness of 0.7 mm polished to a mirror finish was fixed to a substrate fixture 130 provided on the stage 110 of the substrate internal processing apparatus 100 via a fixing table 125. . Note that the substrate 10 fixed to the stage 110 is not limited to a single substrate 10 and may be a plurality.

  And the stage support part 120 which supports the stage 110, the laser light source 160, the condensing lens 170, and the aberration adjustment board 180 were fixed to the anti-vibration base.

The laser light source 160 used was a device that irradiates a pulsed fiber laser (1064 nm) at a wavelength of 1064 nm, a repetition oscillation frequency of 50 kHz, an output of 0.7 W (after the objective lens 170), and a pulse width of 200 ns. The condenser lens 170 had a numerical aperture (NA) of 0.85 and a focal length of 1.2 mm. As the aberration adjusting plate 180, a cover glass having a thickness of 0.15 mm and a refractive index of 1.5 was used. Here, Table 1 shows laser irradiation conditions together with Example 2 and Comparative Example described later.

  The stage 110, the laser light source 160, and the like are controlled by a control device (not shown) to control the position and moving speed of the stage 110 and the stage support 120, and an apparatus for controlling ON / OFF of laser irradiation of the laser light source 160. used.

  Next, the surface of the substrate 10 on the stage 110 is set to have a flatness of ± 3 μm, the stage 110 is moved in a predetermined direction by the stage support unit 120, and the optical axis of the condenser lens 170 of the laser light source 160 is mounted on the rotary stage 110. It was located on the surface peripheral edge side of the substrate 10.

  When the optical axis of the condensing lens 170 is thus positioned on the surface peripheral edge side of the substrate 10, the condensing lens 170 is lowered so that the condensing point P is located on the surface of the substrate 10, and then inside the substrate 10. The aberration adjusting plate 180 was lowered so that the condensing point P for the internal modified layer 14 could be formed, and the condensing lens 170 and the aberration adjusting plate 180 were brought close to the surface of the substrate 10. The distance at this time is 0.3 to 0.4 times the depth of the condensing point P when the depth of the condensing point P is in the range of 0.05 to 0.2 mm.

  Next, the stage 110 is moved so that the trajectory formed by the condensing point P forms a grid-like trajectory 12 with a pitch of 1 μm while controlling the linear velocity of the condensing point P to be 10 mm / second. The drive of the support part 120 was controlled.

  Here, the driving of the stage 110 is suppressed to adjust the linear velocity of the condensing point P to 3 mm / second, and the pitch interval of the laser light 190 is narrowed to 0.5 μm pitch in the vicinity of the surface peripheral portion side of the substrate 10. Thus, the laser beam 190 is intensively irradiated in the immediate vicinity of the peripheral edge of the surface of the substrate 10 to form a separation start region when the surface of the substrate 10 is separated, and after forming the internal modified layer 14, the laser Irradiation of light 190 was stopped.

During the above operation, the stage 110 was reciprocated in a predetermined direction in 10 mm seconds by the stage support section 120. In addition, after the irradiation of the laser beam 190 was stopped, the appearance of the substrate 10 was observed, but the surface remained a mirror finish , and no change was seen in the appearance.

  After the internal modified layer 14 was formed, the substrate 10 was removed from the stage 110, the metal plates 20 and 21 were adhered to both surfaces of the substrate 10 with an adhesive, and the adhesive 25 was cured.

  As the adhesive 25 used in the present embodiment, any adhesive may be used as long as it is stronger than the cohesive force of the polycrystalline grains forming the region near the inner modified layer 14 of the substrate 10. For example, a product name: SOLARLOC, model number: HIK-, which is a two-component room temperature curing type temporary fixing adhesive provided by Denki Kagaku Kogyo Co., Ltd. as a temporary fixing adhesive for solar cells and semiconductor silicon ingot slices. 700M20 can be used. Such an adhesive 25 is disclosed in Patent Document 5 and Patent Document 6.

  When bonding the metal plates 20 and 21 to the substrate 10, the metal plates 20 and 21 are pretreated by scratching the surface of the metal plate (SUS304) to be bonded with sandpaper # 400, wiping with ethanol, and naturally drying. Was given. Thereafter, the adhesive 25 was applied to the substrate 10 or the metal plates 20 and 21 which were cleaned by wiping the surface with ethanol using the attached quantitative mixing mixer gun.

  Then, the spacers 31 were sandwiched at two or more locations so that the coating thickness of the adhesive 25 was 200 μm, a PET film (Toray Lumirror T60) was placed thereon, and a metal plate 20 was placed on the PET film.

  Furthermore, after leaving still at room temperature for 1-2 hours, the metal plate 21 was similarly adhere | attached also on the back surface of the board | substrate 10. FIG. At this time, no PET film is used (there is no process to use). Then, it left still at room temperature for 12 hours or more, and the adhesive agent 25 was hardened completely.

  Through such a series of steps, the structure 40 is formed by bonding the metal plates 20 and 21 to both surfaces of the substrate 10 with the adhesive 25.

  Next, when the structure 40 is mounted on the cleaving device 50 and a predetermined pressing force is applied to the structure 40 with the cleaving jig 54, the substrate 10 included in the structure 40 is placed in the vicinity of the internal reforming layer 14. I was able to split it.

  FIG. 16 is a photograph showing the structure of the internal modified layer 14 that could be cleaved. This photograph was taken with an infrared microscope.

(Example 2)
In Example 1, the output of the laser beam 190 after the objective lens was 0.7 W, but in Example 2, it is set to 0.5 W. Other conditions are the same.

  In this case, similarly to Example 1, the substrate 10 on which the internal modified layer 14 was formed could be cleaved by the cleaving apparatus 50.

  FIG. 17 is a photograph showing a cross-sectional structure of the split surface of the substrate 10. This photograph was taken with a Keyence digital microscope VHX-500.

(Comparative example)
In Example 1, the pulse width is 100 ns, but in this comparative example, the pulse width is 200 ns. Other conditions are the same.

  In this case, as in Example 1, the substrate 10 on which the internal modified layer 14 was formed was cleaved by the cleaving apparatus 50, but cleaving failed.

  FIG. 18 is a photograph showing the structure of the internal modified layer 14 that could not be cleaved. This photograph was taken with an infrared microscope.

(Other embodiments)
As described above, the present invention has been described according to the embodiment. However, it should be understood that the descriptions and drawings constituting a part of this disclosure are illustrative and do not limit the present invention. From this disclosure, various alternative embodiments, examples and operational techniques will be apparent to those skilled in the art.

  For example, in the above-described embodiment, the silicon single crystal substrate is exemplified. However, the present invention can be similarly applied to, for example, silicon carbide (SiC).

  Since the substrate can be efficiently thinned by the substrate processing method of the present invention, the thinly cut substrate can be applied to a solar cell as long as it is a Si substrate, and a sapphire substrate such as a GaN-based semiconductor device. Can be applied to light-emitting diodes, laser diodes, etc., and SiC can be applied to SiC-based power devices, etc., in a wide range of fields such as transparent electronics, lighting, and hybrid / electric vehicles. Applicable.

DESCRIPTION OF SYMBOLS 10 Substrate 14 Internal modification layers 20 and 21 Metal plate 25 Adhesive 50 Cleaving device 52 Base 54 Cleaving jig 100 Substrate internal processing device 110 Stage 120 Stage support 160 Laser light source 170 Condensing lens 180 Aberration adjustment plate

Claims (10)

A substrate processing method for processing a single crystal silicon substrate,
Arranging the laser focusing means on the substrate in a non-contact manner;
Irradiating the surface of the substrate with laser light by the laser condensing means, and condensing the laser light inside the substrate;
A step of relatively moving the laser focusing unit and the substrate to form a modified layer inside the substrate;
The modified layer has polycrystalline grains of polycrystalline silicon in a predetermined depth range from the surface of the substrate, and the modified layer has an asymmetric structure in the depth direction of the substrate. , internal stress have a maximum in the vicinity of an upper portion of the said substrate inside the modified layer,
A substrate processing method characterized by controlling the agglomeration force of the polycrystalline grains in the vicinity of the upper part and dividing the vicinity of the upper part by applying a predetermined force to the substrate.   The substrate processing method according to claim 1, wherein the irradiated laser light has a wavelength of a transmittance of 10% or more at a depth of 500 μm of the substrate.   The substrate processing method according to claim 1, wherein the irradiated laser light has a pulse width of 50 ns or more. 2. The substrate processing method according to claim 1, wherein the surface of the substrate is mirror- finished .   The substrate processing method according to claim 1, wherein in the modified layer, the dimensions of the polycrystalline grains have an asymmetric distribution in the depth direction of the substrate.   The substrate processing method according to claim 1, wherein the polycrystalline layer has a dimension of 150 μm or less in the modified layer. A silicon single crystal substrate processed inside,
A modified layer having polycrystalline silicon polycrystalline grains in a predetermined depth range from the surface of the substrate, the modified layer having an asymmetric structure in the depth direction of the substrate; internal stress have a maximum in the vicinity of an upper portion of the said substrate inside the modified layer,
A substrate characterized by controlling the agglomeration force of the polycrystalline grains in the vicinity of the upper portion so that it can be divided by applying a predetermined force to the substrate in the vicinity of the upper portion . The substrate according to claim 7, wherein the surface of the substrate has a mirror finish .   8. The substrate according to claim 7, wherein in the modified layer, the size of the polycrystalline grains has an asymmetric distribution in the depth direction of the substrate.   The substrate according to claim 7, wherein in the modified layer, the size of the polycrystalline grains is 150 μm or less.