Manufacturing method of element chip and plasma processing method

Abstract

To form a deep groove with a high aspect ratio in a substrate including a compound semiconductor layer.SOLUTION: A plasma processing method includes: a first step of exposing a substrate including a compound semiconductor layer and a mask covering a partial region of a surface of the compound semiconductor layer to first plasma, thereby forming a protective film at a bottom part of a groove corresponding to at least a region of the compound semiconductor layer that is not covered with the mask; a second step of exposing the substrate to second plasma, thereby removing the protective film at the bottom part and exposing the compound semiconductor layer; and a third step of exposing the substrate to third plasma generated from gas containing at least one of chlorine and bromine, thereby removing the compound semiconductor layer exposed to the bottom part of the groove and allowing a reaction product between the compound semiconductor layer and the third plasma to deposit on the groove. In the first step, high-frequency power is applied to a stage where the substrate is placed, so that the reaction product deposited on the groove in the third step is removed.SELECTED DRAWING: Figure 3

Description

[Technical field]

[0001] The present invention relates to a plasma processing method, and more particularly to a method for dicing a substrate provided with a compound semiconductor layer. [Background technology]

[0002] In the fields of dry etching and plasma dicing, the Bosch process for etching silicon layers is known as a cycle etching method as a method for forming deep grooves with a large aspect ratio (ratio of groove depth to width) in a substrate, which is the layer to be processed.

[0003] In the Bosch process, a protective film deposition step, a protective film removal step for removing the protective film deposited on the bottom of the groove, and a process layer etching step are repeatedly performed in this order (see, for example, Patent Document 1). As a result, a protective film is formed on the sidewall of the groove, and while the protective film suppresses etching of the process layer in the surface direction, the process layer is etched in the depth direction, forming a groove with a large aspect ratio in the process layer. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP2014-45610A Summary of the Invention [Problem to be solved by the invention]

[0005] Compound semiconductors such as GaAs, AlGaAs, AlAs, InP, GaP, CdTe, ZnSe, SiC, and GaN have low volatility of etching products compared to silicon and silicon oxide. When forming deep grooves in substrates containing these compound semiconductors using the above-mentioned cycle etching method, etching products may adhere to the side walls of the grooves during etching, narrowing the opening, and reducing the processing accuracy and processing speed.

[0006] For example, when etching a GaAs substrate with plasma, a chlorine-based gas is often used as the etching gas. However, when a cycle etching method is performed on a GaAs substrate using a chlorine-based gas as the etching step of the processed layer, the reaction products of the chlorine-based gas and Ga or As have low volatility, and the reaction products that cannot be discharged outside the groove may adhere to the side walls of the groove and narrow the opening. As a result, the etching speed may decrease, the processing accuracy may decrease, the processed shape of the groove may become tapered, or the etching may not proceed. [Means for solving the problem]

[0007] One aspect of the present invention includes a method for producing a substrate including a compound semiconductor layer having a plurality of element regions and division regions that define the element regions, and a mask that covers the compound semiconductor layer in the element regions and exposes the compound semiconductor layer in the division regions; a mounting step of mounting the substrate on a stage installed in a processing chamber of a plasma processing apparatus; and a singulation step of forming grooves in the compound semiconductor layer that correspond to the division regions by plasma generated inside the processing chamber, and then dividing the substrate into a plurality of element chips having the element regions. In the singulation step, a first plasma generated inside the processing chamber is used to form at least The present invention relates to a method for manufacturing an element chip, which sequentially repeats the following steps: a first step of forming a protective film on the bottom of a groove; a second step of removing the protective film at the bottom by a second plasma generated inside the processing chamber to expose the compound semiconductor layer; and a third step of removing the compound semiconductor layer exposed at the bottom of the groove by a third plasma generated inside the processing chamber from a gas containing at least one of chlorine and bromine, and depositing a reaction product of the compound semiconductor layer and the third plasma on an upper part of the groove; and in the first step, high-frequency power is applied to the stage to remove the reaction product deposited on the upper part of the groove in the third step.

[0008] Another aspect of the present invention relates to a plasma processing method including: a preparing step of preparing a substrate including a compound semiconductor layer and a mask covering a partial region of a surface of the compound semiconductor layer; a placing step of placing the substrate on a stage installed in a processing chamber of a plasma processing apparatus; and a forming step of a groove in the compound semiconductor layer corresponding to a region of the compound semiconductor layer not covered by the mask, wherein in the forming step of the groove, the following steps are sequentially repeated: a first step of exposing the substrate to a first plasma to form a protective film at least on a bottom of the groove; a second step of exposing the substrate to a second plasma to remove the protective film at the bottom and expose the compound semiconductor layer; and a third step of exposing the substrate to a third plasma generated from a gas containing at least one of chlorine and bromine to remove the compound semiconductor layer exposed on the bottom of the groove and deposit a reaction product of the compound semiconductor layer and the third plasma on an upper portion of the groove; and in the first step, a high-frequency power is applied to the stage to remove the reaction product deposited on the upper portion of the groove in the third step. Effect of the Invention

[0009] According to the present invention, it is possible to easily form deep grooves in a compound semiconductor substrate, and to easily separate element chips by, for example, plasma dicing. [Brief description of the drawings]

[0010] [Figure 1] FIG. 1A is a top view showing a schematic diagram of a transport carrier holding a substrate, and FIG. [Diagram 2] 1 is a conceptual diagram showing a cross-sectional structure of a plasma processing apparatus; [Diagram 3] 1 is an example of a flowchart showing a method for manufacturing a component chip (plasma processing method) according to an embodiment of the present invention. [Figure 4] 5 is another example of a flowchart showing the manufacturing method (plasma processing method) of the element chip according to the embodiment of the present invention. [Diagram 5]10 is yet another example of a flowchart showing the method for manufacturing an element chip (plasma processing method) according to an embodiment of the present invention. [Figure 6A] 1 is a SEM photograph of a cross section of a GaAs substrate obtained by forming deep grooves in the substrate using the plasma processing method according to an embodiment of the present invention. [Figure 6B] 1 is a SEM photograph of a cross section of a GaAs substrate in which deep grooves were formed using a conventional plasma processing method. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] One embodiment of the present invention relates to a method for manufacturing element chips, which comprises singulating a substrate having a compound semiconductor layer and dividing the substrate into a plurality of element chips. Specifically, the compound semiconductor layer is provided with a plurality of element regions and division regions that define the element regions. The substrate includes the compound semiconductor layer and a mask that covers the compound semiconductor layer in the element regions and exposes the compound semiconductor layer in the division regions, and the mask forms openings in the division regions.

[0012] The method for manufacturing element chips includes a preparation step of preparing the substrate, a placement step of placing the substrate on a stage installed in a processing chamber of a plasma processing apparatus, and a singulation step of forming grooves corresponding to division regions in the compound semiconductor layer by plasma generated inside the processing chamber, and then dividing the substrate into a plurality of element chips each having an element region. In the singulation step, the substrate is divided into a plurality of element regions by, for example, dicing to obtain element chips. In the singulation step, the following steps (i) to (iii) are sequentially repeated as one cycle.

[0013] Step (i): Protective film formation step A protective film is formed at least on the bottom of the groove by the first plasma generated inside the processing chamber. The protective film has a function of suppressing the compound semiconductor layer on the sidewall of the groove from reacting with the plasma in step (iii) and being etched, thereby preventing the groove from becoming wider.

[0014] Step (ii): Protective film removal step Next, the protective film is removed at the bottom by a second plasma generated inside the processing chamber to expose the compound semiconductor layer.

[0015] Step (iii): Semiconductor layer removal step Next, the compound semiconductor layer exposed at the bottom of the groove is removed by a third plasma generated while a gas containing at least one of chlorine and bromine is supplied into the processing chamber, thereby making the groove deeper. The gas may contain only either chlorine or bromine, or may contain both chlorine and bromine.

[0016] Etching of a compound semiconductor layer is usually performed using an etching gas containing chlorine and / or bromine, such as Cl2 or Br2. However, the reaction products of these etching gases and the compound semiconductor generally have low volatility. Therefore, the deeper the groove, the more likely it is that the reaction products between the compound semiconductor generated at the bottom of the groove and the third plasma cannot diffuse outside the groove and adhere to and accumulate on the sidewall of the groove. The reaction products are particularly likely to adhere to and accumulate on the upper part of the groove (e.g., the sidewall of the mask), narrowing the opening of the groove. As a result, the etching rate decreases, the processed shape of the groove becomes tapered, the deposition of a protective film on the sidewall of the groove is hindered, or etching does not proceed.

[0017] Therefore, in the method of this embodiment, high frequency power is applied to the stage in the above step (i) (protective film forming step). The application of high frequency power generates a self-bias potential between the stage and the plasma, and ions in the plasma are accelerated by the bias potential and collide with the substrate placed on the stage. The collision energy removes reaction products that have accumulated on the upper part of the groove and narrowed the opening. This allows the sidewall surface to be kept nearly vertical in step (iii), and a deeper groove can be processed while maintaining a high aspect ratio. The high frequency power applied to the stage in step (i) may be 25 W or more, 50 W or more, or 75 W or more.

[0018] The method of the present disclosure is not limited to applications for manufacturing element chips, but can also be used for applications for forming deep grooves in a compound semiconductor layer of a substrate. In the plasma processing method of the present embodiment, in the preparation step, a substrate is prepared in which a portion of the surface of the compound semiconductor layer is covered with a mask. An opening is formed in the compound semiconductor layer in the area not covered with the mask. Even in this case, by sequentially repeating the above steps (i) to (iii) as one cycle on this groove, a groove corresponding to the area not covered with the mask of the compound semiconductor layer can be formed in the compound semiconductor layer, and the formed groove can be processed into a deep groove with a high aspect ratio.

[0019] Hereinafter, a method for manufacturing an element chip (plasma processing method) according to an embodiment of the present invention will be specifically described with reference to the drawings. Fig. 1 is a top view (a) showing a schematic diagram of a transport carrier holding a substrate, and a cross-sectional view (b) taken along line BB. Fig. 2 is a conceptual diagram showing a cross-section of the structure of a plasma processing apparatus. However, the present invention is not limited by the configurations of the transport carrier and the plasma processing apparatus.

[0020] (preparation process) First, the substrate 1 to be diced is prepared. The substrate 1 has a first main surface 1X and a second main surface 1Y, and is partitioned into a division region (also called a street St) and a plurality of element regions defined by the division region (neither is shown). The substrate 1 is diced into element chips having element regions by etching the streets St of the substrate 1. Circuit layers such as semiconductor circuits, electronic component elements, and MEMS may be formed in the element regions.

[0021] The substrate 1 includes, for example, a first layer 11 and a second layer 12 which is a semiconductor layer formed on the second main surface 1Y side of the first layer 11. The first layer functions as a mask in the singulation process, and is patterned so as to cover the second layer (semiconductor layer) in the element region and expose the second layer (semiconductor layer) in the division region. The first layer includes, for example, an insulating film, a metal material, a resin protective layer (for example, polyimide), a resist layer, an electrode pad, a bump, and the like. The insulating film may be included as a laminate (multilayer wiring layer) with a metal material for wiring. The insulating film includes, for example, a resin film such as polyimide, silicon dioxide (SiO2), silicon nitride (Si3N4), a low dielectric constant film (Low-k film), and the like. The resist layer includes, for example, a so-called resist material such as a thermosetting resin such as polyimide, a photoresist such as a phenol resin, or a water-soluble resist such as an acrylic resin. The patterning of the first layer can be performed by photolithography, for example, when the first layer is a photoresist. When the first layer is an insulating film or a metal material, the first layer can be patterned by, for example, laser scribing or etching. The second layer is a compound semiconductor layer. Compound semiconductors constituting the compound semiconductor layer include III-V group semiconductors such as GaAs, AlGaAs, AlAs, InP, GaP, and GaN, II-VI group semiconductors such as CdTe and ZnSe, and IV-IV group semiconductors containing multiple IV group elements such as SiC.

[0022] The thickness of the first layer is not particularly limited, and is, for example, 2 to 10 μm. When the first layer includes a secondary wiring layer or a bump, the thickness is, for example, about 200 μm at most. The thickness of the resist layer is also not particularly limited, and is, for example, 5 to 20 μm. The thickness of the second layer is also not particularly limited, and is, for example, 20 to 1000 μm, and may be 100 to 300 μm. The size of the substrate 1 is also not particularly limited, and is, for example, about 50 mm to 300 mm in maximum diameter. The shape of the substrate 1 is also not particularly limited, and is, for example, circular or rectangular. The substrate 1 may be provided with a cutout such as an orientation flat (orientation flat) or a notch (neither of which are shown).

[0023] Here, from the viewpoint of ease of handling, the singulation step described below is preferably performed with the second main surface 1Y of the substrate 1 supported by the support member 3. In this case, in the preparation step, a transport carrier 10 is prepared together with the substrate 1.

[0024] The material of the support member 3 is not particularly limited. In particular, considering that the substrate 1 is diced while being supported by the support member 3, the support member 3 is preferably a flexible resin film in order to facilitate picking up the resulting element chips. Therefore, from the viewpoint of ease of handling, the support member 3 is fixed to the frame 2. Hereinafter, the frame 2 and the support member 3 fixed to the frame 2 will be collectively referred to as the transport carrier 10.

[0025] The material of the resin film is not particularly limited, and examples thereof include thermoplastic resins such as polyolefins such as polyethylene and polypropylene, and polyesters such as polyethylene terephthalate. The resin film may contain various additives such as rubber components (e.g., ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM)) for imparting elasticity, plasticizers, softeners, antioxidants, and conductive materials. The thermoplastic resin may also have a functional group that exhibits a photopolymerization reaction, such as an acrylic group.

[0026] The support member 3 has, for example, a surface having an adhesive (adhesive surface 3a) and a surface not having an adhesive (non-adhesive surface 3b). The outer peripheral edge of the adhesive surface 3a is attached to one surface of the frame 2, covering the opening of the frame 2. The substrate 1 is attached and held on the portion of the adhesive surface 3a exposed from the opening of the frame 2. In the plasma dicing process, the support member 3 is placed on a stage installed in a processing chamber (hereinafter referred to as a vacuum chamber) of a plasma processing apparatus so that the non-adhesive surface 3b comes into contact with the stage.

[0027] The adhesive surface 3a is preferably made of an adhesive component whose adhesive strength decreases when irradiated with ultraviolet (UV) rays. As a result, when picking up the element chip 20 after plasma dicing, the element chip 20 can be easily peeled off from the adhesive surface 3a by irradiating it with UV rays, making it easy to pick up. For example, the support member 3 can be obtained by applying a UV-curable acrylic adhesive to one side of a resin film to a thickness of 5 to 20 μm.

[0028] The frame 2 is a frame having an opening with an area equal to or larger than the entire substrate 1, and has a predetermined width and a substantially constant thin thickness. The frame 2 has a degree of rigidity that allows it to be transported while holding the support member 3 and the substrate 1. The shape of the opening of the frame 2 is not particularly limited, and may be, for example, a circle or a polygon such as a rectangle or a hexagon. The frame 2 may be provided with a notch 2a or a corner cut 2b for positioning. Examples of materials for the frame 2 include metals such as aluminum and stainless steel, and resins.

[0029] The transport carrier 10 is obtained by adhering and fixing the support member 3 to one surface of the frame 2. At this time, as shown in Fig. 1(b), the adhesive surface 3a of the support member 3 faces the frame. Next, the second layer 12 of the substrate 1 is adhered to the adhesive surface 3a of the support member 3, thereby holding the substrate 1 on the transport carrier 10.

[0030] (Placement process) Next, the transport carrier 10 holding the substrate 1 is placed on a stage installed in a vacuum chamber which is a processing chamber of the plasma processing apparatus 100 .

[0031] As shown in FIG. 2, the plasma processing apparatus 100 includes a stage 111. The transport carrier 10 is mounted on the stage 111 so that the surface of the support member 3 that holds the substrate 1 faces upward. The stage 111 is large enough to accommodate the entire transport carrier 10. A cover 124 is disposed above the stage 111, the cover 124 covering at least a portion of the frame 2 and the support member 3 and having a window 124W for exposing at least a portion of the substrate 1. A pressing member 107 is disposed on the cover 124 for pressing the frame 2 when the frame 2 is placed on the stage 111. The pressing member 107 is preferably a member that can come into point contact with the frame 2 (for example, a coil spring or a resin having elasticity). This makes it possible to correct the distortion of the frame 2 while suppressing the heat of the frame 2 and the cover 124 from affecting each other.

[0032] The stage 111 and the cover 124 are disposed in a vacuum chamber 103, which is a processing chamber. The vacuum chamber 103 is generally cylindrical with an open top, and the top opening is closed by a dielectric member 108, which is a lid. Examples of materials constituting the vacuum chamber 103 include aluminum, stainless steel (SUS), and aluminum with anodized surface. Examples of materials constituting the dielectric member 108 include dielectric materials such as yttrium oxide (Y2O3), aluminum nitride (AlN), alumina (Al2O3), and quartz (SiO2). A first electrode 109 is disposed above the dielectric member 108 as an upper electrode. The first electrode 109 is, for example, a coil when the plasma processing apparatus 100 includes an inductively coupled plasma source. The first electrode 109 is electrically connected to a first high frequency power supply 110A. The stage 111 is disposed on the bottom side of the vacuum chamber 103.

[0033] A gas inlet 103a is connected to the vacuum chamber 103. A process gas source 112 and an ashing gas source 113, which are supply sources of gas for generating plasma, are connected to the gas inlet 103a by piping. The vacuum chamber 103 is also provided with an exhaust port 103b, to which a decompression mechanism 114 including a vacuum pump for exhausting gas in the vacuum chamber 103 to reduce the pressure is connected. With the process gas being supplied into the vacuum chamber 103, high frequency power is supplied from a first high frequency power supply 110A to the first electrode 109, whereby plasma is generated in the vacuum chamber 103.

[0034] The stage 111 includes an electrode layer 115 and a metal layer 116, each of which is substantially circular, a base 117 that supports the electrode layer 115 and the metal layer 116, and an outer periphery 118 that surrounds the electrode layer 115, the metal layer 116, and the base 117. The outer periphery 118 is made of a metal that is conductive and resistant to etching, and protects the electrode layer 115, the metal layer 116, and the base 117 from plasma. An annular outer periphery ring 129 is disposed on the upper surface of the outer periphery 118. The outer periphery ring 129 serves to protect the upper surface of the outer periphery 118 from plasma. The electrode layer 115 and the outer periphery ring 129 are made of, for example, the above-mentioned dielectric materials.

[0035] An electrode for electrostatic chuck (hereinafter referred to as ESC electrode 119) and a second electrode 120 electrically connected to the second high frequency power supply 110B are arranged inside the electrode layer 115. By applying high frequency power from the second high frequency power supply 110B to the second electrode 120, it is possible to control the energy when ions in the plasma generated in the vacuum chamber 103 are incident on the substrate placed on the stage. A DC power supply 126 is electrically connected to the ESC electrode 119. The electrostatic chuck mechanism is composed of the ESC electrode 119 and the DC power supply 126. The supporting member 3 is pressed against the stage 111 and fixed thereto by the electrostatic chuck mechanism. Hereinafter, a case where an electrostatic chuck mechanism is provided as a fixing mechanism for fixing the supporting member 3 to the stage 111 will be described as an example, but is not limited thereto. The supporting member 3 may be fixed to the stage 111 by a clamp (not shown).

[0036] The metal layer 116 is made of, for example, aluminum with an alumite coating formed on the surface. A coolant flow path 127 is formed in the metal layer 116. The coolant flow path 127 cools the stage 111. By cooling the stage 111, the support member 3 mounted on the stage 111 is cooled, and the cover 124, a part of which is in contact with the stage 111, is also cooled. This prevents the substrate 1 and the support member 3 from being damaged by being heated during plasma processing. The coolant in the coolant flow path 127 is circulated by a coolant circulation device 125.

[0037] A plurality of supports 122 penetrating the stage 111 are arranged near the outer periphery of the stage 111. The supports 122 support the frame 2 of the transport carrier 10. The supports 122 are driven to move up and down by a lifting mechanism 123A. When the transport carrier 10 is transported into the vacuum chamber 103, it is handed over to the supports 122 that have risen to a predetermined position. When the upper end surface of the supports 122 is lowered to the same level as the stage 111 or lower, the transport carrier 10 is placed at a predetermined position on the stage 111.

[0038] A plurality of lifting rods 121 are connected to the ends of the cover 124, enabling the cover 124 to be raised and lowered. The lifting rods 121 are driven to rise and lower by a lifting mechanism 123B. The operation of lifting and lowering the cover 124 by the lifting mechanism 123B can be performed independently of the lifting mechanism 123A.

[0039] The control device 128 controls the operation of the elements that make up the plasma processing device 100, including the first high frequency power supply 110A, the second high frequency power supply 110B, the process gas source 112, the ashing gas source 113, the pressure reduction mechanism 114, the refrigerant circulation device 125, the lifting mechanism 123A, the lifting mechanism 123B, and the electrostatic adsorption mechanism.

[0040] When the transport carrier 10 is placed on the stage 111, the cover 124 is raised to a predetermined position in the vacuum chamber 103 by driving the lifting rod 121. A gate valve (not shown) opens and the transport carrier 10 is loaded. At this time, the multiple supports 122 are waiting in a raised state. When the transport carrier 10 reaches a predetermined position above the stage 111, the transport carrier 10 is handed over to the supports 122. The transport carrier 10 is handed over to the upper end surfaces of the supports 122 so that the adhesive surface 3a of the support member 3 faces upward.

[0041] When the transport carrier 10 is transferred to the support 122, the vacuum chamber 103 is placed in a sealed state. Next, the support 122 starts to descend. The upper end surface of the support 122 descends to the same level as the stage 111 or lower, so that the transport carrier 10 is placed on the stage 111. Next, the lift rod 121 is driven. The lift rod 121 lowers the cover 124 to a predetermined position. At this time, the distance between the cover 124 and the stage 111 is adjusted so that the pressing member 107 arranged on the cover 124 can make point contact with the frame 2. As a result, the frame 2 is pressed by the pressing member 107, and the parts of the frame 2 and the support member 3 that do not hold the substrate 1 are covered by the cover 124, and the substrate 1 is exposed from the window 124W of the cover 124. It is preferable that the pressing member 107 is a member that can make point contact with the frame 2 (for example, a coil spring or a resin having elasticity). This makes it possible to correct distortion of the frame 2 while suppressing the heat of the frame 2 and the cover 124 from affecting each other.

[0042] The cover 124 is, for example, a doughnut shape having a substantially circular outer contour, and has a certain width and a thin thickness. The inner diameter of the cover 124 (diameter of the window portion 124W) is smaller than the inner diameter of the frame 2, and the outer diameter of the cover 124 is larger than the outer diameter of the frame 2. Therefore, when the transport carrier 10 is mounted at a predetermined position on the stage and the cover 124 is lowered, the cover 124 can cover at least a part of the frame 2 and the support member 3. At least a part of the substrate 1 is exposed from the window portion 124W. The cover 124 is made of, for example, a dielectric material such as ceramics (e.g., alumina, aluminum nitride, etc.) or quartz, or a metal such as aluminum or aluminum whose surface is anodized. The pressing member 107 can be made of a resin material in addition to the above-mentioned dielectric materials and metals.

[0043] After the transport carrier 10 is handed over to the supporting portion 122, a voltage is applied from the DC power supply 126 to the ESC electrodes 119. As a result, the supporting member 3 is electrostatically attracted to the stage 111 at the same time as it comes into contact with the stage 111. Note that the application of the voltage to the ESC electrodes 119 may be started after the supporting member 3 is placed on (comes into contact with) the stage 111.

[0044] (Singulation process) In the singulation process, step (i) (protective film forming step), step (ii) (protective film removing step), and step (iii) (semiconductor layer removing step) are sequentially repeated as one cycle.

[0045] (Protective film formation process) The first plasma used in step (i) (protective film forming step) can be generated from, for example, a gas containing fluorine and carbon (first etching gas). As the gas containing fluorine and carbon (first etching gas), for example, a gas containing C4F8, CH2F2, or CHF3 is preferably used.

[0046] By using the first plasma generated from a gas containing fluorine and carbon, a protective film containing fluorocarbon can be formed on the surface of the substrate, including the sidewalls and bottom of the groove. At this time, a bias potential is generated between the stage and the plasma by applying power to the second electrode 120, and ions in the plasma are accelerated by the bias potential and collide with the substrate placed on the stage. Then, the energy of the collision removes the reaction products that were generated in step (iii) (semiconductor layer removal step) of the previous cycle and accumulated on the sidewalls of the upper part of the groove, narrowing the opening.

[0047] The protective film forming process is performed under the following processing conditions: while supplying C4F8 as a raw material gas at 150 to 600 sccm, the pressure in the processing chamber is adjusted to 1 to 25 Pa, the power applied from the first high frequency power supply 110A to the first electrode 109 is 1500 to 5000 W, the power applied from the second high frequency power supply 110B to the second electrode 120 is 5 to 150 W, and the processing time is 0.1 to 10 seconds.

[0048] Specific examples of conditions for generating the first plasma in step (i) are given below. First etching gas: C4F8 gas Flow rate: 300sccm Total pressure: 5.0Pa Power applied to the first electrode: 2000W Power applied to the second electrode: 50W Processing time: 1 second

[0049] The process (i) (protective film forming process) includes a first step and a second step that follows the first step, and the high frequency power applied to the stage in the first step may be greater than the high frequency power applied to the stage in the second step. In the first step, the reaction products that are generated in the process (iii) (semiconductor layer removing process) of the previous cycle and that adhere to and accumulate on the side walls of the grooves are efficiently removed by applying a higher high frequency power. In the second step, a protective film is formed on the side walls of the grooves in a state where the reaction products have been removed. In the second step, the first plasma is more likely to collide with the side walls of the grooves as well as the bottom of the grooves by applying a lower high frequency power. Therefore, the protective film is more likely to be formed on the side walls of the grooves, and a uniform protective film can be formed on the side walls of the grooves.

[0050] In the first step, the high frequency power applied to the stage is, for example, 25 to 100 W, and may be 25 W or more, 50 W or more, or 75 W or more. In contrast, in the second step, the high frequency power applied to the stage may be, for example, 0 to 20 W. In the second step, high frequency power does not have to be applied to the stage.

[0051] The high frequency power applied to the stage in step (i) (protective film forming step) (if step (i) has a first step and a second step, this refers to the high frequency power applied to the stage in the first step; the same applies below) may be increased continuously or stepwise as the depth of the groove formed in the compound semiconductor layer increases. That is, the high frequency power applied to the stage in step (i) may be changed according to the number of cycles of steps (i) to (iii) performed, and the higher the number of cycles performed, the higher the high frequency power may be increased continuously or stepwise.

[0052] When the number of cycles is small and the depth of the grooves formed in the compound semiconductor layer is shallow, the reaction products generated in step (iii) are easily discharged outside the grooves, and the applied high-frequency power may be small. On the other hand, the more the number of cycles is large and the deeper the grooves formed in the compound semiconductor layer are, the more likely the reaction products generated in step (iii) are to remain in the grooves and adhere to and accumulate on the side walls of the grooves. Therefore, it is preferable to increase the high-frequency power applied to the stage in order to remove the reaction products that have adhered to and accumulated on the side walls of the grooves.

[0053] The high frequency power applied to the stage in step (i) may be changed stepwise according to the depth of the groove formed in the compound semiconductor layer. For example, the relationship between the high frequency power applied to the stage in step (i) and the depth of the groove may be 25 W or more when the groove depth is 40 μm or more, 50 W or more when the groove depth is 70 μm or more, and 75 W or more when the groove depth is 100 μm or more.

[0054] (Protective film removal process) The second plasma used in step (ii) (protective film removal step) may be generated from a gas (second etching gas) containing at least one of chlorine and bromine. The second etching gas may contain only one of chlorine and bromine, or may contain both. The gas species contained in the second etching gas may be at least one selected from the group consisting of HCl, Cl2, BCl3, SiCl4, HBr, Br2, BBr3, and SiBr4. The second etching gas may be one selected from these gas species, or may be a mixed gas containing a plurality of species.

[0055] The protective film removal process can be performed under the following processing conditions: while supplying a mixed gas of BCl3, Cl2, and Ar as a source gas at 100 to 450 sccm, adjusting the pressure in the processing chamber to 1 to 15 Pa, applying a power of 1000 to 5000 W from the first high frequency power supply 110A to the first electrode 109, applying a power of 50 to 400 W from the second high frequency power supply 110B to the second electrode 120, and setting the processing time to 3 to 12 seconds.

[0056] Specific examples of conditions for generating the second plasma in step (ii) are given below. Second etching gas: A mixture of BCl3, Cl2, and Ar Total flow rate: 190sccm BCl3 flow rate: 70sccm Cl2 flow: 60sccm Ar flow rate: 60sccm Total pressure: 3.0Pa Power applied to the first electrode: 1500W Power applied to the second electrode: 200W Processing time: 6 seconds

[0057] (Semiconductor layer removal process) The third plasma used in step (iii) may be generated from a gas (third etching gas) containing at least one of chlorine and bromine. The third etching gas may contain only one of chlorine and bromine, or may contain both. The gas species contained in the third etching gas may be at least one selected from the group consisting of HCl, Cl2, BCl3, SiCl4, HBr, Br2, BBr3, and SiBr4. The second etching gas may be one selected from these gas species, or may be a mixed gas containing a plurality of species.

[0058] The third etching gas may contain the same gas species as the second etching gas. The third etching gas may be composed of the same combination of gas species as the second etching gas, and may have a different mixture ratio (and / or partial pressure ratio) from the second etching gas.

[0059] The semiconductor layer removal process can be performed under the following processing conditions: while supplying a mixed gas of BCl3, Cl2, and Ar as a source gas at 200 to 800 sccm, adjusting the pressure in the processing chamber to 1 to 20 Pa, applying a power of 1000 to 5000 W from the first high frequency power supply 110A to the first electrode 109, applying a power of 20 to 400 W from the second high frequency power supply 110B to the second electrode 120, and setting the processing time to 5 to 30 seconds.

[0060] Specific examples of conditions for generating the third plasma in step (iii) are given below. Third etching gas: a mixture of BCl3, Cl2, and Ar Total flow rate: 380sccm BCl3 flow rate: 70sccm Cl2 flow: 290sccm Ar flow rate: 20sccm Total pressure: 5.0Pa Power applied to the first electrode: 2000W Power applied to the second electrode: 50W Processing time: 15 seconds

[0061] If necessary, an inert gas such as Ar may be added to the first etching gas, the second etching gas, and the third etching gas.

[0062] (Compound semiconductor layer) The compound semiconductor constituting the compound semiconductor layer is a semiconductor material containing at least two elements. Examples of compound semiconductors include III-V group semiconductors such as GaAs, AlGaAs, AlAs, InP, GaP, and GaN, II-VI group semiconductors such as CdTe and ZnSe, and IV-IV group semiconductors containing multiple IV group elements such as SiC. These compound semiconductors are called difficult-to-etch materials because the volatility of the etching products is low compared to silicon and silicon oxide. The method of the present embodiment can be suitably used for forming grooves in these difficult-to-etch materials.

[0063] Fig. 3 shows an example of a flow chart showing a manufacturing method (plasma processing method) of an element chip according to this embodiment. In the example of Fig. 3, first, a substrate having a compound semiconductor layer and a mask is prepared (ST01). The substrate is provided with a plurality of element regions and division regions that define the element regions. The mask covers the compound layer in the element regions. Meanwhile, the compound semiconductor layer is exposed in the division regions, and openings are formed in the division regions by the mask.

[0064] Next, the substrate, while being held by the support member, is placed on a stage installed in the processing chamber of the plasma processing apparatus (ST02).

[0065] Subsequently, the substrate is divided into a plurality of element chips each having an element region, and the substrate is singulated by repeatedly performing a cycle of a protective film forming step ST04, a protective film removing step ST05, and a semiconductor layer removing step ST06. The protective film forming step ST04, the protective film removing step ST05, and the semiconductor layer removing step ST06 correspond to the above-mentioned steps (i) to (iii), respectively, and detailed description thereof will be omitted.

[0066] Before the placement process ST02 and after the first protective film formation process ST04, the number of cycle executions N for singulation is set to 0 (ST03). When the semiconductor layer removal process ST06 is completed, a process of adding 1 to the number of cycle executions N is performed (ST07).

[0067] The number of cycle executions N reflects the depth of the groove formed in the compound semiconductor layer. When N becomes equal to or greater than a predetermined maximum number of cycle executions Nmax, assuming that a groove with a predetermined depth has been formed in the compound semiconductor layer, the process is terminated (YES branch in ST08). On the other hand, when N is less than Nmax, the process returns to ST04 and repeats the cycle consisting of the protective film formation process ST04, the protective film removal process ST05, and the semiconductor layer removal process ST06 (NO branch in ST08).

[0068] FIG. 4 shows another example of a flowchart showing the method for manufacturing an element chip (plasma processing method) of the present embodiment. In the example of FIG. 4, the protective film formation process ST04 consists of a first step ST04A and a second step ST04B. In the first step ST04A, the high-frequency power applied to the stage is greater than the high-frequency power applied to the stage in the second step ST04B.

[0069] FIG. 5 shows still another example of a flowchart showing the method for manufacturing an element chip (plasma processing method) of the present embodiment. In the example of FIG. 5, it is determined whether the number of cycle executions N is equal to or greater than a predetermined value N1 (N1 < Nmax) (ST09). When N = N1, the plasma processing conditions in the subsequent protective film formation process ST04 are changed, and a process (ST10) of increasing the set value of the high-frequency power applied to the stage in the protective film formation process ST04 is performed. After this process, in the protective film formation process, plasma processing is performed with the changed high-frequency power value. Thereby, when the depth of the groove in the compound semiconductor layer is equal to or greater than a predetermined depth corresponding to N1, the high-frequency power applied to the stage in the protective film formation process is increased to facilitate the removal of the reaction products adhering to the side walls of the groove. Thereby, it is possible to efficiently remove the reaction products that become difficult to remove as the groove becomes deeper.

[0070] The present invention will be specifically described below based on examples and comparative examples, but the present invention is not limited thereto.

[0071] Example 1 A GaAs substrate was plasma etched under the conditions shown in Table 1 to form a deep trench. Figure 6A shows an SEM image of the cross section of the substrate cut to separate the device region. Measurements revealed that the trench had a depth of 104.7 μm. The opening width at the top of the trench was 16.7 μm, the trench width at a depth of 40 μm from the surface was 14.6 μm, and the trench width at the bottom was 10.7 μm. Although the trench width at the bottom was smaller than the opening width, the ratio of this reduction to the opening width was kept to 36%.

[0072] Comparative Example 1 A GaAs substrate was plasma etched under the same conditions as in Example 1, except that no high frequency power was applied to the stage in the protective film formation process, to form a deep groove. FIG. 6B shows an SEM photograph of a cross section of the substrate cut to separate the element region. Measurements showed that the groove had a depth of 99.3 μm. The opening width at the top of the groove was 17.2 μm, the groove width at a depth of 40 μm from the surface was 13.5 μm, and the groove width at the bottom was 9.6 μm. Although the groove width at the bottom was smaller than the opening width, the ratio of the reduction to the opening width reached 45%.

[0073] [Table 1] [Industrial Applicability]

[0074] The plasma processing method according to the present invention can be used in an etching process for forming deep trenches in a compound semiconductor layer, and can be particularly used in the manufacture of element chips by dicing a compound semiconductor substrate. [Explanation of symbols]

[0075] 1: Substrate 1X: 1st main surface 1Y: Second main surface 11: 1st layer 12:Second layer 10: Transport carrier 2: Frame 2a:Notch 2b: Corner cut 3: Support member 3a:Adhesive side 3b: Non-adhesive surface 100: Plasma processing device 103: Vacuum chamber 103a: Gas inlet 103b: Exhaust port 107: Clamping member 108: Dielectric member 109: First electrode 110A: First high frequency power source 110B: Second high frequency power source 111: Stage 112: Process gas source 113: Ashing gas source 114: Pressure reduction mechanism 115: Electrode layer 116: Metal layer 117: Foundation 118: Outer periphery 119:ESC electrode 120: second electrode 121: Lifting rod 122: Support part 123A, 123B: Lifting mechanism 124: Cover 124W: Window section 125: Refrigerant circulation device 126:DC power supply 127: Coolant flow path 128: Control device 129: Outer ring

Claims

1. a preparation step of preparing a substrate including a compound semiconductor layer having a plurality of element regions and division regions that define the element regions, and a mask that covers the compound semiconductor layer in the element regions and exposes the compound semiconductor layer in the division regions; a step of placing the substrate on a stage installed in a processing chamber of a plasma processing apparatus; a singulation process in which a groove corresponding to the dividing region is formed in the compound semiconductor layer by plasma generated inside the processing chamber, and then the substrate is divided into a plurality of element chips each including the element region; In the singulation step, a first step of forming a protective film on a sidewall and a bottom of the groove by a first plasma generated inside the processing chamber; a second step of removing the protective film at the bottom by a second plasma generated inside the processing chamber to expose the compound semiconductor layer; a third step of removing the compound semiconductor layer exposed at the bottom of the groove by a third plasma generated from a gas containing at least one of chlorine and bromine inside the processing chamber, and depositing a reaction product of the compound semiconductor layer and the third plasma on the side wall of the upper part of the groove so as to narrow an opening of the groove; The cycle is repeated in sequence, In the first step, high frequency power is applied to the stage; The first process includes a first step and a second step performed subsequent to the first step, the high frequency power applied to the stage in the first step is greater than the high frequency power applied to the stage in the second step; The reaction product deposited on the sidewall of the upper portion of the groove in the third process is removed in the first step of the first process in the next cycle; In the second step of the first process in the next cycle, the protective film is formed on the side wall of the groove in a state in which the reaction product has been removed.

2. The method for manufacturing component chips according to claim 1 , wherein the first plasma is generated from a gas containing fluorine and carbon.

3. 3. The method for manufacturing component chips according to claim 1, wherein the second plasma is generated from a gas containing at least one of chlorine and bromine.

4. 4. The method for manufacturing an element chip according to claim 1, wherein the high-frequency power applied to the stage in the first step is increased continuously or stepwise as the depth of the groove formed in the compound semiconductor layer increases.

5. a preparation step of preparing a substrate including a compound semiconductor layer and a mask covering a partial region of a surface of the compound semiconductor layer; a step of placing the substrate on a stage installed in a processing chamber of a plasma processing apparatus; forming grooves in the compound semiconductor layer corresponding to areas of the compound semiconductor layer that are not covered by the mask; In the step of forming the groove, a first step of forming a protective film on sidewalls and a bottom of the groove by exposing the substrate to a first plasma; a second step of removing the protective film at the bottom by exposing the substrate to a second plasma to expose the compound semiconductor layer; a third step of exposing the substrate to a third plasma generated from a gas containing at least one of chlorine and bromine, thereby removing the compound semiconductor layer exposed at the bottom of the groove and depositing a reaction product of the compound semiconductor layer and the third plasma on the sidewall of the upper part of the groove so as to narrow the opening of the groove; The cycle is repeated in sequence, In the first step, high frequency power is applied to the stage; The first process includes a first step and a second step performed subsequent to the first step, the high frequency power applied to the stage in the first step is greater than the high frequency power applied to the stage in the second step; The reaction product deposited on the sidewall of the upper portion of the groove in the third process is removed in the first step of the first process in the next cycle; In the second step of the first process in the next cycle, the protective film is formed on the side wall of the groove in a state in which the reaction product is removed.

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