CN110581050A - Processing method and plasma processing apparatus - Google Patents
Processing method and plasma processing apparatus Download PDFInfo
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- CN110581050A CN110581050A CN201910475932.4A CN201910475932A CN110581050A CN 110581050 A CN110581050 A CN 110581050A CN 201910475932 A CN201910475932 A CN 201910475932A CN 110581050 A CN110581050 A CN 110581050A
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32431—Constructional details of the reactor
- H01J37/3244—Gas supply means
- H01J37/32449—Gas control, e.g. control of the gas flow
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32431—Constructional details of the reactor
- H01J37/32458—Vessel
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
-
- H01L21/205—
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J2237/00—Discharge tubes exposing object to beam, e.g. for analysis treatment, etching, imaging
- H01J2237/32—Processing objects by plasma generation
- H01J2237/33—Processing objects by plasma generation characterised by the type of processing
- H01J2237/332—Coating
- H01J2237/3321—CVD [Chemical Vapor Deposition]
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Drying Of Semiconductors (AREA)
Abstract
The invention provides a technique capable of improving the control performance of selective processing. In one embodiment, there is provided a method of processing an object to be processed in a processing container, including: a first step of selectively forming a first film on a surface of an object to be processed disposed in a processing vessel by plasma vapor deposition; and a second step of forming a second film by atomic layer deposition in a region where the first film is not present. The second step forms a second film by repeatedly performing a process including: a third step of supplying a precursor gas into the processing container to form a precursor layer on the surface of the object to be processed; a fourth step of purging the inside of the process container after the third step; a fifth step of transforming the precursor layer into a second film by exposing the precursor to a modifying plasma within the process vessel after the fourth step; and a sixth step of purging the space inside the process container after the fifth step. The processing method may be performed by a plasma processing apparatus.
Description
Technical Field
embodiments of the present invention relate to a processing method and a plasma processing apparatus.
Background
As device dimensions shrink, Atomic scale processing such as Atomic Layer Deposition (ALD) becomes more demanding. Patent document 1 discloses a technique of selectively forming a film at the bottom of a pattern using plasma-based modification and atomic layer deposition.
Documents of the prior art
Patent document
Patent document 1: U.S. patent application publication No. two 017/0140983 specification
disclosure of Invention
Technical problem to be solved by the invention
The invention provides a technique capable of improving the control performance of selective processing.
Technical solution for solving technical problem
In one exemplary embodiment, a method of processing an object to be processed is provided. The processing method comprises the following steps: a first step of selectively forming a first film on a surface of an object to be processed disposed in a processing container by plasma chemical vapor deposition; and a second step of forming a second film by atomic layer deposition in a region where the first film is not present.
In one exemplary embodiment, a method of processing an object to be processed is provided. The processing method comprises the following steps: a step of supplying an object to be processed into the processing container; a first step of selectively forming a first film on the surface of the object to be processed by plasma chemical vapor deposition; and a second step of forming a second film by atomic layer deposition on the surface of the object to be processed where the first film is not present. In the second step, a precursor gas is supplied into the process container, a precursor layer is formed on a region of the object to be processed where the first film is not present, the interior of the process container is purged, and the precursor is exposed to a modifying plasma in the process container to convert the precursor layer into the second film, thereby reducing the film thickness of the first film by the modifying plasma.
In one exemplary embodiment, a plasma processing apparatus is provided. The plasma processing apparatus includes: a processing container for accommodating an object to be processed; and a control unit that controls a process performed on the object to be processed in the processing container, wherein the control unit includes a flow execution unit that repeatedly executes a flow including: a first process of selectively forming a first film on a surface of an object to be processed disposed in a processing container by plasma chemical vapor deposition; and a second process of forming a second film by atomic layer deposition in a region where the first film does not exist in the surface.
effects of the invention
As described above, the controllability of the selective processing can be improved.
Drawings
Fig. 1 is a flowchart showing a processing method according to an embodiment.
Fig. 2 is a diagram showing an example of the configuration of a plasma processing apparatus for executing the method shown in the flowchart of fig. 1.
Fig. 3 (a) is a diagram showing a state of the object to be processed before the flow shown in fig. 1 is executed, fig. 3 (b) is a diagram showing a state of the object to be processed during the execution of the flow shown in fig. 1, and fig. 3 (c) is a diagram showing a state of the object to be processed after the execution of the flow shown in fig. 1.
Fig. 4 (a) is a diagram showing a state of the membrane before the flow shown in fig. 1 is executed, fig. 4 (b) is a diagram showing a state of the membrane during the execution of the flow shown in fig. 1, and fig. 4 (c) is a diagram showing a state of the membrane after the execution of the flow shown in fig. 1.
fig. 5 shows a change in the film thickness of the second film in the case where the method shown in the flowchart of fig. 1 is employed.
Fig. 6 shows another case of change in the film thickness of the second film in the case of using the method shown in the flowchart of fig. 1.
Fig. 7 (a) is a diagram showing an example of a state of the first film formed by isotropic plasma, and fig. 7 (b) is a diagram showing an example of a state of the first film formed by anisotropic plasma.
Fig. 8 is a diagram for explaining a mode of forming and removing a film in the case where the first film is formed by anisotropic plasma.
Fig. 9 is a diagram for explaining a mode of forming and removing a film in the case where the first film is formed by anisotropic plasma.
fig. 10 is a diagram for explaining a mode of forming and removing a film in the case where the first film is formed by anisotropic plasma.
Fig. 11 is a diagram for explaining a mode of forming and removing a film in the case where the first film is formed by anisotropic plasma.
fig. 12 shows an example of the form of the first film and the second film in the case where the second film is formed by unsaturated atom deposition by the treatment method shown in fig. 1.
Fig. 13 shows another example of the form of the first film and the second film in the case where the second film is formed by unsaturated atom deposition by the processing method shown in fig. 1.
Fig. 14 is a flowchart showing an example of a processing method in the case where the second region is etched after the second film is formed.
Fig. 15 is a diagram for explaining an example of the processing method shown in fig. 14.
Fig. 16 is a diagram for explaining an example of the processing method shown in fig. 14.
Fig. 17 (a) is a diagram for explaining a relationship between the temperature of the object to be processed and the film formation amount, and fig. 17 (b) is a diagram showing a state in which the object to be processed is divided into a plurality of regions.
Description of the reference numerals
10 … … plasma processing apparatus, 12 … … processing container, 12e … … exhaust port, 12g … … carrying-in/out port, 14 … … support, 18a … … first plate, 18b … … second plate, 22 … … dc power supply, 23 … … switch, 24 … … refrigerant flow path, 26a … … piping, 26b … … piping, 28 … … gas supply line, 30 … … upper electrode, 32 … … insulating shield member, 34 … … electrode plate, 34a … … gas discharge hole, 36 … … electrode support, 36a … … gas diffusion chamber, 36b … … gas through hole, 36c … … gas inlet port, 38 … … gas supply pipe, 40 … … gas source group, 42 … …, 45 valve group 45 … … flow controller group, 46 … … deposit shield, 48 … … exhaust plate, 50 … … exhaust apparatus, 52 … … exhaust pipe, 52a … … gas inlet port, 54 … … gate valve, 62 … … first high frequency power supply, 64 … … second high frequency power supply, 66 … … matching box, 68 … … matching box, 70 … … power supply, 82 … … gas supply tube, CP … … center part, CS … … flow execution part, Cnt … … control part, EP … … edge part, ESC … … electrostatic chuck, FR … … focus ring, G1 … … second gas, HP … … heater power supply, HT … … temperature adjustment part, R1 … … region, R2 … … region, R3 … … region, LE … … lower electrode, Ly1 … … layer, Ly2 … … layer, M1 … … first film, M2 … … second film, MT … … method, P1 … … plasma, PD … … stage, SF … … surface, SF1 … … surface, SF2 … … surface, SF3 … … surface, Sp … … processing space, W … … wafer, ZN … … region.
Detailed Description
Hereinafter, various embodiments will be described in detail with reference to the drawings. In the drawings, the same or corresponding portions are denoted by the same reference numerals.
Fig. 1 is a flowchart illustrating a method of processing an object to be processed (hereinafter, sometimes referred to as a wafer W) according to an embodiment. Method MT is one embodiment of a processing method. The method MT is performed by a plasma processing apparatus.
Fig. 2 shows an example of a plasma processing apparatus according to an embodiment used in the method MT. Fig. 2 schematically shows a cross-sectional structure of a plasma processing apparatus 10 that can be used in various embodiments of the method MT. The plasma processing apparatus 10 includes a processing container 12 having an electrode of a parallel flat plate type. The processing container 12 accommodates wafers W. The processing container 12 has a substantially cylindrical shape, and forms a processing space Sp. The processing container 12 is made of, for example, aluminum, and the inner wall surface thereof is subjected to anodic oxidation treatment. The processing container 12 is grounded for safety.
a substantially cylindrical support portion 14 is provided at the bottom of the processing container 12. The support portion 14 is made of, for example, an insulating material. The support portion 14 extends in the vertical direction from the bottom of the processing container 12. Further, a mounting table PD supported by the support portion 14 is provided.
The stage PD holds the wafer W on its upper surface. The mounting table PD has a lower electrode LE and an electrostatic chuck ESC. The lower electrode LE includes a first plate 18a and a second plate 18 b. The first plate 18a and the second plate 18b are made of metal such as aluminum, and have a substantially circular disk shape. The second plate 18b is disposed on the first plate 18a and electrically connected to the first plate 18 a.
An electrostatic chuck ESC is provided on the second plate 18 b. The electrostatic chuck ESC has a structure in which an electrode as a conductive film is disposed between a pair of insulating layers or between a pair of insulating sheets. The dc power supply 22 is electrically connected to the electrode of the electrostatic chuck ESC via the switch 23. The electrostatic chuck ESC attracts the wafer W by an electrostatic force such as a coulomb force generated by a dc voltage from the dc power supply 22.
A focus ring FR is disposed on the peripheral edge of the second plate 18b so as to surround the edge of the wafer W and the electrostatic chuck ESC. The focus ring FR is provided to improve the uniformity of etching. The focus ring FR is made of a material selected in accordance with the material of the film to be etched, and may be made of quartz, for example.
The second plate 18b is provided with a refrigerant flow path 24 inside. The refrigerant flow path 24 is a part of the temperature adjustment mechanism. The coolant is supplied to the coolant flow field 24 from a cooling device (not shown) provided outside the process container 12 through a pipe 26 a. The refrigerant supplied to the refrigerant passage 24 is returned to the cooling device through the pipe 26 b. In this way, the refrigerant is supplied to the refrigerant flow path 24 so as to circulate. By controlling the temperature of the coolant, the temperature of the wafer W can be controlled.
Further, a gas supply line 28 is provided in the plasma processing apparatus 10. The gas supply line 28 supplies a heat transfer gas, e.g., He gas, from the heat transfer gas supply mechanism between the upper surface of the electrostatic chuck ESC and the back surface of the wafer W.
The plasma processing apparatus 10 is provided with a temperature adjustment unit HT such as a heater. The temperature adjustment portion HT is buried in the second plate 18 b. The heater power supply HP is connected to the temperature adjustment portion HT. The temperature of the electrostatic chuck ESC and thus the wafer W can be adjusted by supplying power from the heater power supply HP to the temperature adjusting unit HT. The temperature adjustment unit HT may be built in the electrostatic chuck ESC.
further, the plasma processing apparatus 10 includes an upper electrode 30. The upper electrode 30 is disposed above the mounting table PD so as to face the mounting table PD. The lower electrode LE and the upper electrode 30 are disposed substantially parallel to each other. A processing space Sp for performing plasma processing on the wafer W is formed between the upper electrode 30 and the lower electrode LE.
The upper electrode 30 is supported on the upper portion of the processing chamber 12 via an insulating shielding member 32. The upper electrode 30 may include an electrode plate 34 and an electrode support 36. The electrode plate 34 faces the processing space Sp and is provided with a plurality of gas exhaust holes 34 a. Electrode plate 34, in one embodiment, comprises silicon.
The electrode supporter 36 supports the electrode plate 34 in such a manner that the electrode plate 34 can be detached. The electrode support 36 is made of a conductive material such as aluminum. The electrode support 36 may have a cooling structure. A gas diffusion chamber 36a is provided inside the electrode support 36. A plurality of gas circulation holes 36b communicating with the gas discharge holes 34a extend from the gas diffusion chamber 36a to the processing space Sp. Further, a gas inlet 36c for introducing the process gas into the gas diffusion chamber 36a is formed in the electrode support 36, and a gas supply pipe 38 is connected to the gas inlet 36 c.
the plasma processing apparatus 10 includes a first high-frequency power supply 62 and a second high-frequency power supply 64. The first high-frequency power source 62 generates first high-frequency power for plasma generation, and generates high-frequency power having a frequency of 27 MHz to 100 MHz (60 MHz in one example). The first high-frequency power source 62 is connected to the upper electrode 30 via a matching unit 66. The matching unit 66 is a circuit for matching the output impedance of the first high-frequency power source 62 with the input impedance on the load side (lower electrode LE side). The first high-frequency power source 62 may be connected to the lower electrode LE via a matching unit 66.
The second high-frequency power supply 64 is a power supply for generating second high-frequency power for introducing ions into the wafer W, and generates high-frequency bias power having a frequency in the range of 400[ kHz ] to 40.68[ MHz ] (in one example, 13.56[ MHz ]). The second high-frequency power supply 64 is connected to the lower electrode LE via a matching unit 68. The matching unit 68 is a circuit for matching the output impedance of the second high-frequency power supply 64 with the input impedance on the load side (lower electrode LE side).
In addition, the plasma processing apparatus 10 may further include a power supply 70. The power source 70 is connected to the upper electrode 30. The power supply 70 applies a voltage for introducing positive ions in the processing space Sp into the electrode plate 34 to the upper electrode 30. In one example, the power supply 70 generates a negative dc voltage. When such a voltage is applied from the power supply 70 to the upper electrode 30, positive ions in the processing space Sp are introduced into the electrode plate 34. By causing the introduced ions to collide with the electrode plate 34, secondary electrons and/or silicon are released from the electrode plate 34.
An exhaust plate 48 is provided between the support portion 14 and the side wall of the processing chamber 12. The exhaust plate 48 can be formed by covering an aluminum material with Y2O3And the like. An exhaust port 12e is provided below the exhaust plate 48. The exhaust port 12e is connected to an exhaust device 50 through an exhaust pipe 52, and reduces the pressure in the processing space Sp. A loading/unloading port 12g for the wafer W is provided in a side wall of the processing container 12, and the loading/unloading port 12g is opened and closed by a gate valve 54.
The gas source group 40 has a plurality of gas sources. The valve block 42 includes a plurality of valves. The flow controller group 45 includes a plurality of flow controllers such as mass flow controllers.
the plasma processing apparatus 10 may have a post-mixing structure in which a pipe for supplying a highly reactive gas such as an aminosilane-based gas and a pipe for supplying another gas are independently supplied to the processing space Sp, and the supplied gases are mixed in the processing space Sp. The post-mixing structure includes a gas supply pipe 38 and a gas supply pipe 82. The gas supply pipe 38 and the gas supply pipe 82 are connected to a gas source group 40 via a valve group 42 and a flow rate controller group 45. With the post-mixing structure of the plasma processing apparatus 10, the gas line connected to the gas supply pipe 38 and the gas line connected to the gas supply pipe 82 are independent of each other in the path from the gas source block 40 to the valve block 42. In this case, the gas flowing through the gas supply pipe 38 and the gas flowing through the gas supply pipe 82 are not mixed before being supplied into the processing container 12.
The electrode support 36 is provided with a gas inlet 36 c. The gas inlet 36c is provided above the stage PD. The gas inlet 36c is connected to a first end of a gas supply pipe 38. A second end of the gas supply tube 38 is connected to a valve block 42. The gas is introduced into the gas diffusion chamber 36a formed in the electrode support 36 through the gas introduction port 36 c.
A gas inlet 52a is provided in a side wall of the processing container 12. The gas introduction port 52a is connected to a first end of the gas supply pipe 82. A second end of the gas supply tube 82 is connected to the valve block 42.
In the plasma processing apparatus 10, a deposition shield 46 is detachably provided along the inner wall of the processing vessel 12. A deposit shield 46 is also provided on the outer periphery of the support portion 14. The deposit shield 46 is used to inhibit deposits from adhering to the process vessel 12. By covering the aluminum with Y2O3And the like.
In addition, the plasma processing apparatus 10 may further include a control part Cnt. The controller Cnt controls the process performed on the wafer W in the processing container 12. The control unit Cnt is a computer including a processor, a storage unit, an input device, a display device, and the like, and controls each part of the plasma processing apparatus 10. The control unit Cnt is connected to the valve block 42, the flow rate controller group 45, the exhaust device 50, the first high-frequency power source 62, the matching unit 66, the second high-frequency power source 64, the matching unit 68, the power source 70, the heater power source HP, and the like. The control unit Cnt may be further connected to a refrigerant flow rate, a refrigerant temperature, and the like from the cooling device.
The control unit Cnt includes a flow execution unit CS. The flow execution unit CS operates by a program based on the input processing recipe, and transmits a control signal. The selection of the gas supplied from the gas source group 40, the flow rate of the gas, the exhaust of the exhaust device 50, the supply of electric power from the first high-frequency power source 62 and the second high-frequency power source 64, and the application of voltage from the power source 70 can be controlled by the control signal from the control unit Cnt. The control unit Cnt can also control the power supply of the heater power supply HP, the refrigerant flow rate and the refrigerant temperature from the cooling device, and the like. The steps of the method for processing the wafer W described in the present specification can be executed by operating each part of the plasma processing apparatus 10 under the control of the flow execution unit CS of the control unit Cnt. The flow execution unit CS operates each part of the plasma processing apparatus 10 to execute the processing shown in the method MT in fig. 1.
Referring to fig. 1, a method MT is explained. Next, an example in which the plasma processing apparatus 10 is used to carry out the method MT will be described. In the following description, reference is made to fig. 4, 5, and 6. Fig. 4 is a diagram showing a state of the object to be processed after executing the steps of the method MT. The method MT includes step ST1 (first step, first process), step ST5 (second step, second process), and step ST 4. Fig. 4 and 5 correspond to the case where step ST1a (cleaning process) is not performed in step ST1, and fig. 6 corresponds to the case where step ST1a is performed in step ST 1.
the horizontal axes shown in fig. 5 and 6 represent the time from the start of the method MT. The vertical axes shown in fig. 5 and 6 show the film thickness of the first film M1 and the film thickness of the second film M2. A line LP1 (solid line) shown in each of fig. 5 and 6 indicates a change in film thickness of the second film M2 formed on the surface SF 2. A line LP2 (broken line) shown in each of fig. 5 and 6 indicates a change in film thickness of the first film M1 formed on the surface SF 2. The first film M1 formed on the surface SF2 includes: a first film M1 formed on the surface SF2 by performing a first (initial) step ST 1; and a first film M1 formed on the surface of the second film M2 on the surface SF2 by performing each step ST1 after the second time.
A line LP3 (broken line) shown in each of fig. 5 and 6 indicates a change in film thickness of the first film M1 formed on the surface SF 1.
The thickness TH1a shown in each of fig. 4, 5, and 6 is the maximum value of the thickness of the first film M1 formed on the surface SF1 by performing step ST1 for the first time. The thickness TH1b shown in each of fig. 4, 5, and 6 is the maximum value of the thickness of the first film M1 formed on the surface SF2 by performing step ST1 for the first time.
The thickness TH2 shown in each of fig. 4, 5, and 6 is the thickness of the first film M1 on the surface SF1 at the time when the line LP1 starts rising (time TMb in the case of fig. 4 and 5, and time TMa2 in the case of fig. 6). The thickness TH3 shown in each of fig. 4, 5, and 6 is the thickness of the first film M1 on the surface SF1 at the time when the step ST5 ends (the time when the step ST1 is started again).
First, a wafer W having a surface SF is prepared. The wafer W is placed on the stage PD in the processing chamber 12 of the plasma processing apparatus 10.
The wafer W has a surface SF. As shown in fig. 4 (a) to 4 (c), the surface SF includes a surface SF1 of the first region (region R1) and a surface SF2 of the second region (region R2). The region R1 is included in the wafer W except for the region R2. The region R1 and the region R2 may be formed of the same material. For example, the region R1 and the region R2 are formed using the same material containing silicon.
In another example, each of the region R1 and the region R2 may be formed of different materials. In this case, the region R1 may be a photoresist, a metal-containing mask, a hard mask, or the like. These regions R1 may be made of any of silicon, organic matter, and metal. Specific examples of the material of the region R1 may be any of Si, SiC, an organic film, a metal (W, Ti, WC, or the like), SiON, SiOC.
on the other hand, the region R2 may be an etched film etched through the patterned region R1. Specific example of the region R2 may be SiO2SiON, SiOC, SiN.
In the method MT, step ST1 is first performed. The time TMa1 shown in fig. 4, 5 and 6 indicates the time when step ST1 is started when the method MT is started, and indicates the time when step ST5 ends during the execution of the method MT (the time when step ST1 is restarted).
in step ST1, after the step of supplying the wafer W into the processing container 12 is performed, the first film M1 is selectively formed on the surface SF of the wafer W disposed in the processing container 12 by plasma chemical vapor deposition (plasma CVD). Specifically, a film forming gas and an inert gas are supplied into the processing chamber 12, and a high-frequency power is supplied to generate plasma from the supplied gases. The first film M1 is formed on the surface SF1 of the region R1 of the wafer W by the generated plasma. Further, a first film M1 is formed on the surface SF2 of the region R2 of the wafer W ((a) of fig. 4). The first film M1 formed in the region R1 is thicker than the first film M1 formed in the region R2.
A carbon-containing gas may also be used in step ST 1. For example, when a fluorocarbon gas is used, a fluorocarbon film is formed as the first film M1. Further, for example, when a fluorinated hydrocarbon gas is used, a fluorinated hydrocarbon film is formed as the first film M1. Further, for example, when a hydrocarbon gas is used, a hydrocarbon gas is formed as the first film M1. The first membrane M1 was hydrophobic. Therefore, the precursor layer is not formed on the first film M1, and the second film M2 is not formed in the subsequent step ST 5.
step ST1 may include a cleaning process (step ST1a) of removing the first film M1 on the surface SF2 (fig. 6). In this way, in step ST1, after the first film M1 is formed on the front surface of the wafer W, the first film M1 on the front surface of the wafer W can be removed. An oxygen-containing gas such as CO may be used in step ST1a2A plasma of gas.
Subsequently, step ST5 is performed. The time TMa2 shown in fig. 4, 5 and 6 indicates the time (the time when step ST1 ends) when step ST5 is started after step ST 1.
The step ST5 includes a flow SQ1 and a step ST 3. The step ST5 forms the second film M2 by atomic layer deposition in a region where the first film M1 does not exist in the surface SF of the wafer W. More specifically, step ST5 forms the second film M2 by atomic layer deposition on the surface SF exposed in the surface SF of the wafer W. The region where the first film M1 does not exist is a region where the first film M1 is not formed in step ST5 in the surface SF of the wafer W. The region where the first film M1 is not present can further include: the first film formed at step ST1 in the surface SF of the wafer W passes through the plasma treatment before step ST5 or the region removed at step ST 5. The process SQ1 includes: step ST2a (third step), step ST2b (fourth step), step ST2c (fifth step), and step ST2d (sixth step). By repeating sequence SQ1, the second film M2 is formed on the surface SF of the wafer W. Step ST1 and step ST5 constitute a flow SQ 2.
Flow SQ1 represents 1 cycle of atomic layer deposition. Fig. 3 shows a series of steps of a typical atomic layer deposition. Atomic layer deposition a precursor layer (layer Ly1 shown in (b) of fig. 3) is formed on the surface of the wafer W using plasma P1 of a second gas G1 (precursor gas). Next, the processing space Sp is purged to remove the unadsorbed second gas G1. Next, the precursor layer is changed by using the modified plasma to form an atomic layer deposition layer (layer Ly2 shown in fig. 3 (c)). Subsequently, the process space Sp is selectively purged.
In sequence SQ1, step ST2a supplies a second gas G1 into the processing container 12 to form a precursor layer on the region (e.g., the surface SF2) of the wafer W where the first film M1 is not present. The second gas G1 is chemically adsorbed (chemisorption) on the surface of the wafer W to form a precursor layer. As the second gas G1, any of an aminosilane-based gas, a silicon-containing gas, a titanium-containing gas, a hafnium-containing gas, a tantalum-containing gas, a zirconium-containing gas, and an organic matter-containing gas can be used. In step ST2a, the plasma of the second gas G1 may be generated or the plasma of the second gas G1 may not be generated.
in step ST2b, the process space Sp is purged. The second gas G1 in a gas phase state was removed by purging. For example, in step ST2b, an inert gas such as argon or nitrogen is supplied into the processing container and purged. In this step, the gas molecules excessively adhering to the inner surface OPa of the opening OP are also removed, and the precursor layer becomes a monolayer.
In step ST2c, the precursor layer is converted (modified) into atomic layers (part of the second film M2) by exposing the precursor to a modifying plasma within the processing vessel 12. In this stepA third gas is used that transforms the precursor layer into a thin film. The third gas may be any one of an oxygen-containing gas, a nitrogen-containing gas, and a hydrogen-containing gas. The third gas may, for example, comprise O2Gas, CO2Gas, NO gas, SO2gas, N2Gas, H2Gas and NH3Any of the gases. In step ST2c, the third gas is supplied into the processing space Sp. High-frequency power is supplied from the first high-frequency power source 62 and/or the second high-frequency power source 64, and plasma (modified plasma) of the third gas is generated. The generated modifying plasma modifies the precursor layer. Further, a part of the first film M1 was removed by the reformed plasma, and the film thickness of the first film M1 was reduced. Thus, even if the first film M1 is formed on the surface SF2 in step ST1, the first film M1 can be removed from the surface SF2 by performing SQ 11 or more times. At this time, the film thickness of the first film M1 formed on the surface SF1 also decreases.
Next, step ST2d purges the process space Sp. Specifically, the third gas supplied in step ST2c is discharged. For example, in step ST2d, inert gas such as argon or nitrogen gas may be supplied to the processing space Sp and exhausted. However, SQ1 may not include step ST2 d.
as described above, by performing 1 cycle of the flow SQ1, the layer constituting the second film M2 can be formed on the surface SF2 by one layer. By repeating the sequence SQ1, the second film M2 can be formed on the surface SF2 exposed by removing the first film M1.
In the case shown in fig. 4 and 5, the time TMb indicates a time when the first film M1 on the surface SF2 is completely removed and the surface SF2 is exposed by performing step ST5 (flow SQ 1). In the case shown in fig. 6, the time TMa2 indicates the time when the first film M1 on the surface SF2 is completely removed to expose the surface SF2 before step ST5 is performed by performing step ST1a in step ST 1.
The first film M1 on the surface SF1 is also removed during the execution of step ST 5. Therefore, as shown in fig. 5 and 6, the value of the thickness TH3 of the first film M1 at the end of the execution of step ST5 is smaller than the value of the thickness (the thickness TH1a in the case of fig. 5 and the thickness TH2 in the case of fig. 6) of the first film M1 at the start of the execution of step ST 5. In addition, in the case of fig. 5, the value of the thickness TH2 of the first film M1 on the surface SF1 at the time TMb is smaller than the value of the thickness TH1a of the first film M1 on the surface SF1 at the time TMa2 at the start step ST 5.
Time TMc shown in fig. 5 and 6 indicates a time when the first film M1 on the surface SF1 is removed to expose the surface SF1 and the second film M2 starts to be formed on the surface SF 1. A line LP4 (chain line) shown in each of fig. 5 and 6 indicates a change in the film thickness of the second film M2 on the surface SF1 when the second film M2 starts to be formed on the surface SF1 after time TMc.
With reference to fig. 5, a change in the film thickness of the first film M1 and the second film M2 in the flow SQ1 will be described. Through step ST1, a first film M1 is formed on the surface SF1 and the surface SF2, respectively. At time TMa2 in the case of fig. 5 and at time TMa3 in the case of fig. 6, first film M1 having thickness TH1a is formed on surface SF1 (line LP3), and first film M1 having thickness TH1b is formed on surface SF2 (line LP 2).
The speed of film formation of the first film M1 on the surface SF1 (the inclination of the line LP3 in step ST 1) is faster (larger inclination) than the speed of film formation of each of the first film M1 and the second film M2 on the surface SF2 (the inclination of the line LP2 in step ST1, the inclination of the line LP1 in step ST 5).
In the case of fig. 5, by the subsequent step ST5, the first film M1 on the surface SF1 is removed and the film thickness is reduced. In the case of fig. 6, the first film M1 on the surface SF1 is removed and the film thickness is reduced by step ST1a (cleaning) starting at time TMa3 during execution of step ST1 and step ST5 following step ST 1. On the other hand, by repeating the sequence SQ1, the first film M1 is removed from the surface SF2, and thereafter, the second film M2 is formed on the surface SF 2.
by repeating the sequence SQ1, the first film M1 on the surface SF1 is removed, and at the end of step ST5, the first film M1 remains on the surface SF1 or the surface SF1 is exposed. A second film M2 was formed on the surface SF 2. Therefore, as shown in fig. 4, at the time TMa1 at which step ST5 ends, the thickness TH3 of the first film M1 on the surface SF1 is smaller than the value of the thickness TH2, or 0.
Next, in the method MT, it is determined in step ST3 whether or not to end the flow SQ 1. Specifically, in step ST3, it is determined whether or not the number of repetitions of sequence SQ1 has reached a predetermined number.
If it is determined in step ST3 that the number of repetitions of sequence SQ1 has not reached the preset number (no in step ST 3), sequence SQ1 is repeated. On the other hand, if it is determined that the number of repetitions of the flow SQ1 has reached the preset number (yes in step ST 3), the flow SQ1 is ended. Thus, the method MT repeats step ST5 a plurality of times (sequence SQ 1).
the number of times of repeating SQ1 can be determined according to the thickness of the first film M1. In one embodiment, the timing at which a portion of the first film M1 on the surface SF1 remains may be determined. In another embodiment, the number of times the flow SQ1 is repeated may be set based on the time TMc at which the first film M1 is removed from the surface SF 1.
In the method MT, the flow SQ2 is executed 1 or more times. By repeating the sequence SQ2, as shown by the line LP3 in fig. 5, the first film M1 is formed on the first film M1 on the SF 1. As shown by a line LP1 of fig. 5, a second film M2 is continuously formed on the surface SF 2. The sequence SQ2 is repeated until the thickness of the second film M2 reaches the target thickness. In the flow SQ2, the first film M1 is formed again by step ST1, and the second film M2 is further formed by step ST 5. Step ST1 and step ST5 can be continuously performed in the same processing container (processing container 12) while keeping a vacuum state.
Next, in the method MT, it is determined in step ST4 whether or not to end the flow SQ 2. More specifically, in step ST4, it is determined whether or not the number of repetitions of sequence SQ2 has reached a predetermined number.
if it is determined in step ST4 that the number of repetitions of sequence SQ2 has not reached the preset number (no in step ST 4), sequence SQ2 is repeated. On the other hand, if it is determined in step ST4 that the number of repetitions of sequence SQ2 has reached the preset number (yes in step ST 4), the sequence SQ2 is terminated.
the number of times of repetition of the flow SQ2 is determined based on the target film thickness of the second film M2 on the surface SF 2. That is, the film thickness of the second film M2 can be adjusted by setting the number of times of repetition of the sequence SQ 2.
In another embodiment, step ST5 may also be continued after 2 times of elapse of time TMa 1. In this case, the first film M1 on the surface SF1 is removed in step ST5, and step ST5 is also repeated after exposure. As a result, the second film M2 can be formed also on the surface SF 1. On the other hand, the second film M2 was formed on the surface SF2, and became a thicker second film M2.
In another embodiment, after the first film M1 is formed in step ST1, step ST1a of cleaning the wafer W may be performed. When step ST1a is performed, a part of the first film M1 formed on the surface SF of the wafer W is removed, and the surface SF2 is exposed. By adopting such a manner, the formation of the second film M2 on the surface SF2 is started immediately after the start of step ST5 (fig. 6 shows a change in film thickness of the second film M2 formed on the surface SF2 of the region R1). In this case, TMa and TMb are at the same time.
Further, in another example, in step ST1, by changing the conditions of plasma CVD, the first film M1 different in film thickness can be formed on the surface SF1 and the surface SF 2.
For example, in fig. 7 (a), the first film M1 is formed thicker at the upper portion of the pattern, and the first film M1 becomes thinner toward the bottom portion of the pattern. In fig. 7 (b), a first film M1 is formed on the upper and bottom of the pattern. The first film M1 formed on the upper portion may be thicker than the first film formed on the bottom portion. The first film M1 was hardly formed on the Sidewall (Sidewall) portion of the pattern. The patterns shown in fig. 7 (a) and 7 (b) may be formed by etching before the method MT is performed.
With reference to fig. 8, a description will be given of a mode in which the anisotropic plasma conditions are used in step ST 1. A pattern is provided on the surface SF of the wafer W. The pattern is formed by etching before the method MT is performed. Here, the region R1 is an upper region (low aspect ratio region). The region R2 is a bottom region (high aspect ratio region). In this example, the surface of the region R1 is referred to as surface SF1, and the surface of the region R2 is referred to as surface SF 2. As shown in state CD1, the first film M1 is formed thick on the surface SF1, and the first film M1 is formed thin or the first film M1 is not formed on the surface SF 2. The state CD1 shows an example where the first film is not formed on the surface SF 2.
The state CD1 represents a case where the first film M1 is formed on the surface SF1 by performing step ST 1. The first film M1 is provided only on the surface SF 1. In the case where the first film M1 is formed on a surface other than the surface SF1 (for example, the surface SF2 or the like) by step ST1, the first film M1 formed on the surface other than the surface SF1 is removed by using oxygen-containing plasma or the like, and is referred to as a state CD1 (step ST1 a).
The state CD2 indicates the state of the wafer W before the end of the first step ST5 and the second step ST 1. In step ST5, the first film M1 is partially removed and thinned. By the atomic layer deposition in step ST5, a second film M2 was formed on the side wall and the bottom.
Reference is next made to fig. 9. The state CD3 shows the state of the wafer W at the second time TMa after the second step ST1 after the state CD2 and the start of ST 5. In the state CD3, the first film M1 is formed again by step ST1 for the second time.
The state CD4 indicates the wafer W at the time TMa (before the third execution of step ST 1) after the second step ST5 after the state CD 3. The first film M1 is removed to be thinned through step ST 5. At the bottom of the pattern (region R2), the second film M2 is formed thicker by step ST 5. Flow SQ2 may be performed multiple times until the second film M2 is of a desired thickness. Compared with the case where the first film M1 is formed thick at one time, the opening is not blocked (region R1), so that the subsequent step ST5 (atomic layer deposition) can be performed with good control performance.
Fig. 10 shows still another embodiment. The pattern used in this embodiment is formed by etching performed before the method MT. The etching and process MT can be performed continuously in the same processing vessel. The state CD5 shows the state of the wafer W when the first film M1 is provided in the region R1 on the upper side of the structure (feature) and the region R2 on the bottom side of the structure in the first step ST 1. The first film M1 is formed on the surface SF1 and the surface SF 2.
The state CD6 indicates the wafer W before the second step ST1 after the first step ST5 (time TMa) is performed on the state CD 5. In the state CD6, the first film M1 on the surface SF1 is thinned by being removed in step ST 5. On the other hand, the first film M1 on the surface SF2 was removed to expose the surface SF 2. On the other hand, on the side wall of the structure (surface SF3), a second film M2 is formed.
The state CD7 shown in fig. 11 indicates the wafer W in the case where step ST5 is continued even after the state CD 6. When step ST5 is performed, the first film M1 on the surface SF1 is removed to be exposed. A second film M2 was formed on the surface SF 2. The second film M2 on surface SF3 is thicker than the second film M2 on surface SF 2.
The state CD8 shown in fig. 11 indicates the wafer W in the case where step ST5 is continued even after the state CD 7. On the surface SF1 exposed in the state CD7, a second film M2 is formed by step ST 5. The second film M2 on the surface SF3, the second film M2 on the surface SF2, and the second film M2 on the surface SF1 become thinner in this order. In this way, the second film M2 having different thicknesses can be formed in each region of the region R1, the region R2, the region R3, and the like. Here, the example of the anisotropic plasma is described, and when the first film M1 is formed by the isotropic plasma, the second film having a film thickness that differs from region to region can be similarly formed by repeating step ST 5.
Although the example in which the first film M1 is further formed after the state CD6 to form the second film having a different film thickness has been described above, the present invention is not limited to this example, and the region R2 may be etched after the state CD 6. In this manner, since the second film M2 is formed on the side wall (surface SF3) of the structure, bowing (bowing) during etching can be suppressed. Method MT and subsequent etching can be performed in the same processing vessel. By adopting such a manner, the productivity can be improved.
(modification 1: deposition of unsaturated atom)
in step ST5, the second film M2 can be partially conformally formed by making the formation of the precursor layer of the surface of the wafer W unsaturated in step ST2a and/or by making the conversion of the precursor layer to the second film M2 unsaturated in step ST2 c. That is, the formation of the second film M2 of step ST5 may also be performed by unsaturated atom deposition. The unsaturated atom deposition satisfies any one of the following (a) to (c).
(a) The adsorption of the second gas G1 for forming the precursor layer in the region of the wafer W where the first film M1 does not exist is not saturated.
(b) Is the modified unsaturation of the second gas G1 adsorbed in the region of the wafer W where the first film M1 does not exist.
(c) The adsorption of the second gas G1 and the modification of the second gas G1 adsorbed in the region of the wafer W where the first film M1 is not present are unsaturated.
The unsaturated atoms are not completely modified in some cases, except for the case where the second gas G1 is not adsorbed to the entire surface. The second film can be formed partially conformally by unsaturated atom deposition. More specifically, the second film M2 can be formed thick on the upper portion of the pattern, and the second film M2 can be formed thin toward the bottom of the pattern. In addition, the steps, conditions, and the like for the deposition of unsaturated atoms can be made the same as those of the above-described ordinary atomic deposition, except for the matters (a) to (c) described above. Therefore, even in the case where the unsaturated atomic deposition is performed instead of the normal atomic deposition in step ST5, a part of the first film M1 can be removed by the third gas in step ST2c, and the film thickness of the first film M1 can be reduced or eliminated.
Fig. 12 and 13 show modification 1 in which the second film M2 is formed in step 5 by unsaturated atom deposition. The pattern used in modification 1 is formed by etching performed before the method MT. The etching and process MT may be performed continuously in the same processing vessel (e.g., processing vessel 12). The state CD9 shows the state of the wafer W when the first film M1 is provided in the region R1 on the upper side of the structure (feature) and the region R2 on the bottom side of the structure in the first step ST 1. The first film M1 is formed on the surface SF1 and the surface SF 2.
the state CD10 indicates the wafer W before the second step ST1 after the first step ST5 (time TMa1) is performed on the state CD 9. In the state CD10, the first film M1 on the surface SF1 is thinned by being removed in step ST 5. On the other hand, the first film M1 on the surface SF2 was removed to expose the surface SF 2. Further, a second film M2 was formed on the side wall of the structure (surface SF 3). In modification 1, since the formation of the second film M2 in step ST5 is performed by unsaturated atomic deposition, the second film M2 is formed thickly on the upper portion of the pattern, and the second film M2 becomes thinner as going to the bottom portion of the pattern. In the state CD9, the second film M2 was not formed at the pattern bottom regardless of the presence or absence of the first film M1.
The state C11 shown in fig. 13 represents the wafer W in the case where the step ST5 is continued after the state CD 10. When step ST5 is performed, the first film M1 on the surface SF1 is removed to expose the surface SF 1.
The state CD12 shown in fig. 13 indicates the wafer W in the case where step ST5 is continued even after the state CD 11. In the state C12, the second film M2 is formed on the surface SF1 exposed by the step ST 5.
in this way, by performing the formation of the second film M2 in step ST5 by unsaturated atomic deposition, the formation position and film thickness of the second film M2 can be further adjusted.
(modification 2: Change of processing conditions in accordance with the thickness of the first film M1)
When the step ST5 and the step of etching the wafer W in the processing container 12 after the step ST5 (step ST6 shown in fig. 14 described later) are repeatedly performed, the position and thickness of the second film M2 can be changed by changing the process conditions of the step ST 5. In other words, although the example in which the first film M1 is further formed and the second film M2 is formed after the state CD10 has been described above, the present invention is not limited to this example, and the region R2 may be etched after the state CD 10. Further, the etching of the region R2 and the flows SQ1 and SQ2 may be repeated. In this manner, since the second film M2 is formed on the side wall (surface SF3) of the structure, it is possible to suppress shape abnormality such as bowing during etching.
Fig. 14 is a flowchart showing an example of a processing method in the case where the region R2 is etched after the second film M2 is formed. Fig. 15 and 16 are diagrams for explaining an example of the processing method shown in fig. 14.
The state CD13 shown in fig. 15 corresponds to the state CD10 in fig. 12, and shows the state of the wafer W before etching the region R2. The first film M1 is formed on the surface SF1, and the second film M2 is partially conformally formed on the sidewalls (surface SF 3). The second film M2 is formed to cover a portion directly below the first film M1 where the shape abnormality is likely to occur due to etching.
the state CD14 shows the state after the first etching ST6 was performed on the state CD 13. The first film M1 is formed on the surface SF1, and the second film M2 is partially conformally formed on the sidewalls (surface SF 3). The inner wall of the second film M2 is removed by etching. When the steps ST5 and ST6 are further repeatedly executed from the state CD14, the top of the first film M1 is gradually removed, and the distance from the top of the first film M1 to the surface SF2 of the region R2 to be etched changes (state CD 15). In this case, when the second film M2 is formed without changing the processing conditions of steps ST2a and ST2c, the second film M2 is formed at a position lower than the position directly below the first film M1 where the shape abnormality is generated.
Then, the modification 2 judges whether or not the film thickness of the first film MT1 is the predetermined value after the etching (step ST6) and the step ST7 (step ST 8). The determination as to whether or not the film thickness of the first film M1 is the predetermined value may be made based on the film thickness of the first film M1 before the execution of step ST5 and the number of times of execution of step ST5 and step ST 6. When it is judged that the film thickness of the first film M1 is the predetermined value (yes at step ST8), the processing conditions of step ST2a and step ST2c are set again (step ST 9). For example, when the process conditions are set so that the coverage in step ST2a is changed in the depth direction of the pattern, the process conditions are changed so that the second gas G1 is adsorbed only in the upper portion of the pattern. For example, the processing time of the next step 2a is shorter than the processing time of the immediately preceding step ST2 a. For example, when the process conditions are set so that the coverage in step ST2c is changed in the depth direction of the pattern, the process conditions are changed so that the third gas reacts only at a position closer to the upper part of the pattern. For example, the temperature of the process chamber is reduced. On the other hand, when it is judged that the film thickness of the first film M1 is not the predetermined value (no at step ST8), the process returns to step ST5 without changing the processing conditions.
By adjusting the processing conditions in accordance with the film thickness of the first film M1 in this manner, the second film M2 can be selectively formed at a portion where the shape abnormality is likely to occur. For example, in the state CD15, the thickness of the first film M1 is about half of the thickness at the start of the process, and the distance from the top to the region R1 to be etched becomes shorter. In this case, the process conditions are changed to shorten the depth-direction distance for forming the second film M2. Thus, as in the state CD16, the second film M2 can be continuously formed at a position immediately below the first film M1 where the shape abnormality is likely to occur.
in addition, even when the shape abnormality occurs in the region R1 to be etched, the pattern shape can be corrected by updating the processing conditions and executing step ST 5.
further, when the aspect ratio of the pattern is increased by the etching (step ST6), the processing conditions of step ST2a and step ST2c may be changed in accordance with the increase in the aspect ratio. For example, the amount of transport of the radicals generated in step ST2c may be increased. That is, as the number of times of etching (step ST6) increases, the processing conditions are changed so that the position where the second film M2 is formed is at the upper portion of the region R1 of the etching object. However, as for the processing conditions, different processing conditions may be set for each time when the step ST2a and the step ST2c are repeated, or different processing conditions may be adopted after the step ST2a and the step ST2c are repeated a plurality of times. Further, the process conditions may be changed as appropriate depending on factors other than the first film M1.
(modification 3: adjustment of film thickness in wafer surface)
In modification 1 and modification 2, the coverage and film thickness of the second film M2 were adjusted by adjusting the process conditions. However, the processing conditions in step ST2a and step ST2c can be adjusted in the following two points of view.
(1) The film formation position in the depth direction of the pattern is controlled by controlling the dose.
(2) the film thickness of the second film M2 formed was controlled.
In modification 1 and modification 2, the film formation position is controlled mainly from the viewpoint of (1) above. Modification 3 further adjusts the processing conditions in the above point (2). That is, in step ST5, the temperature of the mounting table PD on which the wafer W is mounted is controlled to be different depending on the position, and the thickness of the second film M2 to be formed can be changed in accordance with the temperature of the mounting table PD. Fig. 17 is a diagram for explaining a relationship between the temperature of the object to be processed (e.g., wafer W) and the film deposition amount. The horizontal axis of fig. 17 represents the temperature [ ° c ] of the wafer W, and the vertical axis of fig. 17 represents the film formation amount [ nm ]. The wafer W to be processed in the substrate processing apparatus (e.g., the plasma processing apparatus 10) has a disk shape with a diameter of about 300[ mm ], for example. It is known that when a film deposition process is performed on a wafer W, the film deposition amount changes depending on the temperature of the wafer W. Fig. 17 (a) shows the relationship between the temperature of the wafer W and the film deposition amount. As shown in fig. 17 (a), the film formation amount increases as the temperature of the wafer W increases, and decreases as the temperature of the wafer W decreases.
On the other hand, the following tendency is known: when a process such as etching is performed, the CP shape abnormality (e.g., bowing) becomes small in the center portion of the wafer W, and the EP shape abnormality becomes large in the edge portion of the wafer W (see fig. 17B).
then, in modification 3, as shown in fig. 17 (B), the configuration is such that: the stage (electrostatic chuck) of the wafer W is divided into a plurality of concentric zones ZN, and the temperature of each zone ZN can be independently controlled. The temperature of the center portion CP, which tends to have an abnormally small shape, is controlled to be lower than the edge portion EP, which tends to have an abnormally large shape. By controlling in this manner, the film thickness of the protective film to be formed can be adjusted in accordance with the position of the wafer W in the radial direction, and the in-plane uniformity of the size of the opening to be formed can be improved.
Further, as shown in fig. 17 (B), a plurality of zones ZN divided in the radial direction and the circumferential direction are provided for film thickness control, and the temperature control can be independently performed for each zone ZN. For example, it is also possible to realize a process of forming openings of different shapes by changing the thickness of the protective film formed at each position of the wafer W.
Next, a plurality of specific examples of the processing conditions that can be used in step ST1, step ST2a, and step ST2c are described in example 1 and example 2.
(example 1) plasma CVD was performed in step ST 1. The surface SF of the wafer W comprises SiO2A film and a Si mask disposed thereon.
< step ST1 >
Pressure in the treatment space Sp: 20[ mTorr ]
Power of the first high-frequency power source 62: 300[ W ]
Power of the second high-frequency power supply 64: 0[ W ]
First gas flow rate: c4F6Gas (30 sccm]) Ar gas (300 sccm])
Temperature of the wafer W: 40 deg.C
Execution time: 15[ seconds ]
< step ST2a >
Pressure of the treatment space Sp: 100[ mTorr ]
Power of the first high-frequency power source 62: 0[ W ]
Power of the second high-frequency power supply 64: 0[ W ]
First gas flow rate: aminosilicone-based gas (50 sccm)
Temperature of the wafer W: 10 DEG C
Execution time: 15[ seconds ]
< step ST2c >
Pressure of the treatment space Sp: 200[ mTorr ]
Power of the first high-frequency power source 62: 300[ W ]
Power of the second high-frequency power supply 64: 0[ W ]
First gas flow rate: CO 22Gas (300 sccm])
Temperature of the wafer W: 10 DEG C
Execution time: 10[ seconds ]
(example 2) in example 2, anisotropic plasma CVD was performed in step ST 1. By means of arrangements on the waferSiO of surface SF of W2The Si mask on the film is demarcated.
< step ST1 >
pressure of the treatment space Sp: 30[ mTorr ]
Power of the first high-frequency power source 62: 0[ W ]
Power of the second high-frequency power supply 64: 25[ W ]
First gas flow rate: c4F6gas (40 sccm]) Ar gas (1000 sccm])
Temperature of the wafer W: 60 degree C
Execution time: 15[ seconds ]
< step ST2a >
Pressure of the treatment space Sp: 200[ mTorr ]
power of the first high-frequency power source 62: 0[ W ]
Power of the second high-frequency power supply 64: 0[ W ]
First gas flow rate: aminosilane-based gas (100 sccm)
Temperature of the wafer W: 60 degree C
Execution time: 15[ seconds ]
< step ST2c >
Pressure of the treatment space Sp: 200[ mTorr ]
Power of the first high-frequency power source 62: 500[ W ]
power of the second high-frequency power supply 64: 0[ W ]
First gas flow rate: CO 22Gas (300 sccm])
Temperature of the wafer W: 60 degree C
Execution time: 2[ seconds ]
In the above method MT, the plasma generated in step ST1 may be either anisotropic or isotropic, and may be adjusted according to the film thickness distribution of the second film M2. In another embodiment, when the flow SQ2 is repeated, the step ST1 of performing anisotropic plasma CVD and the step ST1 of performing isotropic plasma CVD may be repeated. In another mode, during the first execution of step ST1, anisotropic plasma CVD and isotropic plasma CVD may be performed in sequence. Further, the CVD conditions of step ST1 at the m-th time (m is a positive integer) may be made different from the CVD conditions of step ST1 at the m + 1-th time. In this manner, the formation site of the first film M1 can be changed, and the film thickness distribution of the first film M1 can be formed.
In the above-described method MT, various changes can be made to the conditions of the plasma CVD performed in step ST 1. Here, a case where a pattern is provided on the surface of the wafer W by etching is considered. The pattern has low aspect ratio regions and high aspect ratio regions. In one embodiment, the gas type of the first gas used in step ST1 may be changed. As the first gas, for example, C can be used4F6Gas or C4F8A gas. C4F6Gas adhesion coefficient greater than C4F8The adhesion coefficient of the gas. Thus, when using C4F6In this case, the first film M1 is formed more on the front surface side (low aspect ratio region) of the wafer W. On the other hand, when C is used4F8At this time, the first film M1 is formed more on the bottom side (high aspect ratio region). In this way, since the adhesion coefficient differs depending on the gas type, the formation position of the first film M1 can be controlled by changing the gas type.
Further, the power of the second high-frequency power supply 64 may also be changed. In one example, the power can be turned on/off. In another example, the value of the power may be varied between a high value and a low value. When the value of the electric power is increased, the first film M1 is formed thickly at the level (upper surface and bottom) of the structure as shown in fig. 7 (b). On the other hand, the first film M1 formed on the side wall is thin. When the value of the electric power is decreased, the first film M1 is formed more on the upper side.
In another embodiment, the wafer temperature at step ST1 can be changed. When the temperature at the time of execution of step ST1 becomes relatively high, the first film M1 is formed more on the bottom side (high aspect ratio region). When the temperature at the step ST1 becomes relatively low, the first film M1 is formed more on the surface side (low aspect ratio region) of the wafer W.
further, the pressure at step ST1 can be changed. The plasma generated when the pressure is relatively high is made isotropic. A thicker first film M1 is formed on the surface side (low aspect ratio region) of the wafer W by isotropic plasma. On the other hand, when the pressure is relatively lowered, the generated plasma is anisotropic. A thicker first film M1 is formed on the bottom side (high aspect ratio region) with anisotropic plasma.
Further, by changing the power of the first high-frequency power source 62 at the time of execution of step ST1, the dissociation state of the plasma can be changed. Therefore, by changing the power, the kind of radicals generated or the radical ratio is changed, and the adhesion coefficient when the first film M1 is formed is changed.
In the above-described method MT, the conditions of step 5 can be variously changed. In one example, the execution time of step ST2c (the time at which plasma is generated) can be changed. By this change, the removal amount of the first film M1 can be adjusted.
Further, in step ST2c, the power of the second high-frequency power supply 64 can be changed. When the power of the second high-frequency power supply 64 is relatively increased, the first film M1 of the horizontal portion (upper surface, bottom) of the structure (feature) is more removed. When the electric power of the second high-frequency power supply 64 is relatively reduced, the amount by which the side wall portion (sidewall) of the structure in the first film M1 is removed increases.
In addition, in step ST2c, the pressure in the processing container 12 can be changed. When the pressure is relatively increased, the ion energy in the plasma becomes small, enabling a mainly isotropic reaction to occur. When the pressure is relatively reduced, the ion energy in the plasma becomes large, enabling mainly anisotropic reactions to occur. Therefore, the region where the first film M1 was removed and the amount of removal of each region can be adjusted by changing the pressure.
Further, at the execution of step ST2c, the power of the first high-frequency power source 62 can be changed. When the power is relatively increased, the plasma density can be increased.
As described above, when the steps ST1 and ST5 are repeatedly executed, the 1 or more conditions described above in step ST1 or ST5 may be different between the m-th (m is a positive integer) execution and the m + 1-th execution. In the case where the flow SQ1 is repeatedly executed to selectively form the second film M2 in the region R2, the execution of the nth time (n is a positive integer) and the execution of the (n + 1) th time may be different from each other for the 1 or more conditions in step ST2 c. In this way, controllability of film formation of the first film M1 and/or the second film M2 can be improved.
By adjusting the execution time of step ST2a within a range of, for example, 2 seconds to 10 seconds, the removal amount of the first film M1 can be controlled. In this case, the removal amount of the first film M1 was 1[ nm ] per 1 cycle of the sequence SQ1]The following (e.g., 0.1[ nm ]]～0.5[nm]) And (4) finishing. Further, the second film M2 contains SiO2In the case of (1), the deposition amount of the second film M2 is a monoatomic layer (i.e., about 0.2 nm) per 1 cycle of the sequence SQ 1. For example, 10[ nm ] is provided as the first film M1]For left and right fluorocarbons, a 10-100 cycle sequence SQ1 is performed to remove the first film M1 and form 2-20 [ nm ]]Left and right second films M2. The first gas for forming the first film M1 may be selected according to the application, and may include a CF-based gas, a CHF-based gas, a CO gas, a CH gas, and the like.
The method MT can also execute step ST1 and step ST5 in processing containers of different plasma processing apparatuses. Step ST1 forms a first film M1 in a region R1 of the wafer W by chemical vapor deposition using plasma of a first gas in the first processing container. Step ST5 forms a second film M2 by atomic layer deposition in a region R2 in the surface of the wafer W where the first film M1 is not formed, within the second processing container. The method MT repeatedly performs step ST1 and step ST 5.
The method MT of the above-described embodiment can be executed using an Inductively Coupled Plasma (Inductively Coupled Plasma) Plasma processing apparatus. The plasma processing apparatus 10 includes the same gas supply system (gas source group 40, valve group 42, flow rate controller group 45, gas supply pipe 38, gas supply pipe 82, and the like) as the plasma processing apparatus.
The above-described method MT may be performed alone, but the wafer W may be etched and patterned in the processing chamber 12 before the method MT is performed. In another embodiment, the wafer W may be etched in the processing container 12 after the method MT is performed. The process MT and etching may be continuously performed in the same processing vessel while maintaining vacuum. In another embodiment, the method MT and the etching may be repeated in the same processing chamber. Since the object to be processed can be processed in the same processing container without being transported, the throughput can be improved. Alternatively, the method MT and etching can be performed using different processing vessels. In this case, the plasma excitation method for the method MT and the plasma excitation method for etching may be different.
while various embodiments have been described above, it will be apparent to those skilled in the art that the present invention can be modified in arrangement and detail without departing from the principle thereof. The present invention is not limited to the specific configuration described in the present embodiment. Therefore, all modifications and changes within the scope of the claims and the spirit thereof belong to the scope of the claims of the present invention.
Claims (18)
1. A method for processing an object to be processed, comprising:
A step of supplying an object to be processed into the processing container;
A first step of selectively forming a first film on the surface of the object to be processed by plasma chemical vapor deposition; and
A second step of forming a second film by atomic layer deposition in a region where the first film is not present.
2. the process of claim 1, wherein:
The first step and the second step are repeatedly performed.
3. The processing method according to claim 1 or 2, characterized by:
The region where the first film is not present is a region where the first film is not formed in the first step.
4. the process of claim 3, wherein:
The region where the first film is not present further comprises: a region of the first film formed in the first step is removed in the plasma treatment before the second step or in the second step.
5. The process according to any one of claims 1 to 4, characterized in that:
In the first step, after the first film is formed on the surface, the first film on the surface of the object to be processed is removed.
6. The process according to any one of claims 1 to 5, characterized in that:
Repeatedly performing a flow in the second step to form the second film,
the process comprises the following steps:
a third step of supplying a precursor gas into the processing container to form a precursor layer on the surface of the object to be processed;
A fourth step of purging the space inside the process container after the third step;
A fifth step, after the fourth step, of transforming the precursor layer into the second film within the processing vessel by exposing the precursor to a modifying plasma; and
A sixth step of purging the space inside the process container after the fifth step.
7. The process according to any one of claims 1 to 5, characterized in that:
The second step is a step of repeatedly executing the flow,
The process comprises the following steps:
A third step of supplying a precursor gas into the processing container to form a precursor layer on the surface of the object to be processed;
A fourth step of purging the space inside the process container after the third step;
A fifth step, after the fourth step, of transforming the precursor layer into the second film within the processing vessel by exposing the precursor to a modifying plasma; and
A sixth step of purging the space inside the process container after the fifth step,
the formation of the precursor layer on the surface of the object to be processed is unsaturated in the third step and/or the conversion of the precursor layer to the second film is unsaturated in the fifth step, whereby the second film is partially conformally formed.
8. The processing method according to claim 6 or 7, characterized by:
The precursor gas is any of an aminosilane-based gas, a silicon-containing gas, a titanium-containing gas, a hafnium-containing gas, a tantalum-containing gas, a zirconium-containing gas, and an organic matter-containing gas,
The modified plasma is generated from any of an oxygen-containing gas, a nitrogen-containing gas, and a hydrogen-containing gas.
9. The process according to any one of claims 6 to 8, characterized in that:
In the case of repeatedly executing the flow, the condition of the fifth step is different between the nth execution and the (n + 1) th execution, where n is a positive integer.
10. the process of any one of claims 1 to 9, wherein:
The first step and the second step are continuously performed in the same processing vessel in a state where a vacuum is maintained.
11. The process according to any one of claims 1 to 10, characterized in that:
in the second step, the temperature of a mounting table on which the object to be processed is mounted is controlled to be different depending on the position, and the thickness of the second film to be formed is changed depending on the temperature of the mounting table.
12. The process of any one of claims 1 to 11, further comprising:
A step of etching the object to be processed in the processing container before the first step; and
a step of etching the object to be processed in the processing container after the second step.
13. The process of claim 12, wherein:
In the case of repeatedly performing the second step and the step of etching the object to be processed in the processing vessel after the second step, the position and thickness of the second film are changed by changing the conditions of the second step.
14. The process according to any one of claims 6 to 12, characterized in that:
In the case where the first step and the second step are repeatedly executed, the condition of the first step is different between the m-th execution and the m + 1-th execution, where m is a positive integer.
15. A method for processing an object to be processed, comprising:
A first step of selectively forming a first film on a surface of an object to be processed disposed in a processing container by plasma chemical vapor deposition; and
A second step of forming a second film by atomic layer deposition on the surface of the object to be processed where the first film is not present,
In the second step, the first step is carried out,
Supplying a precursor gas into the processing container to form a precursor layer in a region of the object where the first film is not present,
Purging the interior of the process vessel,
Transforming the precursor layer into a second film within the processing vessel by exposing the precursor to a modifying plasma,
The modified plasma reduces the film thickness of the first film.
16. The process of claim 15, wherein:
Repeating the first step and the second step.
17. The process of claim 15, wherein:
The second film has different film thicknesses in respective regions of the surface.
18. A plasma processing apparatus, comprising:
A processing container for accommodating an object to be processed; and
A control unit for controlling the processing of the object to be processed in the processing container,
The control section includes a flow execution section that repeatedly executes a flow,
The process comprises the following steps:
a first process of selectively forming a first film on a surface of the object to be processed disposed in the processing container by using plasma chemical vapor deposition; and
A second process of forming a second film by atomic layer deposition in a region where the first film is not present in the surface.
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