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  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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  • C23C16/509—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using radio frequency discharges using internal electrodes
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  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/56—After-treatment
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  • 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
  • H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
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  • H01J37/321—Radio frequency generated discharge the radio frequency energy being inductively coupled to the plasma
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  • H10D30/6891—Floating-gate IGFETs characterised by the shapes, relative sizes or dispositions of the floating gate electrode
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  • H10D64/035—Manufacture or treatment of data-storage electrodes comprising conductor-insulator-conductor-insulator-semiconductor structures

Definitions

• Silicon dot forming method and apparatus and silicon dot and insulating film forming method and apparatus
• the present invention relates to a method and an apparatus for forming micro-sized silicon dots (so-called silicon nanoparticles) used as electronic device materials, light emitting materials, and the like.
• the present invention also relates to a method and apparatus for forming a silicon dot and a substrate with an insulating film formed by overlapping silicon dots and an insulating film, which can be used in a semiconductor device such as a MOS capacitor or a MOS FET.
• a method for forming silicon dots As a method for forming silicon dots, a physical method for forming silicon by heating and evaporating it in an inert gas using an excimer laser or the like is known, and a vapor deposition method in a gas is also known. Yes (see Kanagawa AIST Research Report No.9 / 2003, pages 77-78). The latter is a technique of heating and evaporating silicon by high frequency induction heating or arc discharge instead of laser.
• Japanese Patent Application Laid-Open No. 2004-179658 describes a method of forming silicon dots on a heated substrate by sequentially introducing silane and dichlorosilane as material gases into a CVD chamber.
• a silicon dot is grown from the nucleus through a step of forming a nucleus for growing a silicon dot on a substrate.
• a method of thermally oxidizing a target substrate for forming an insulating film to form an insulating thermal oxide film for example, a silicon substrate is formed at 800 ° C to 900 ° C.
• a method for forming an insulating silicon oxide film by performing thermal oxidation at a high temperature for example, see the above-mentioned Japanese Patent Application Laid-Open No. 2004-179658. Therefore, the selection range of the substrate material is narrowed.
• an insulating film forming method by a plasma CVD method is also known in which an insulating film forming gas is turned into plasma and an insulating film is formed on the substrate at a relatively low temperature under the plasma.
• the plasma CVD method is a force that has been known for a long time to produce capacitively coupled plasma using parallel plate electrodes. Since it is not suitable for plasma processing such as film formation on a substrate with a large area, an antenna is installed outside or inside the plasma generation chamber, and high frequency power is applied to the antenna to induce it from the plasma generation chamber gas. One that generates coupled plasma is drawing attention.
• an internal antenna type inductively coupled plasma CVD apparatus in which an antenna is arranged in a plasma generation chamber has attracted attention from the viewpoint of improving the utilization efficiency of input power.
• This type of plasma CVD apparatus is described in, for example, Japanese Patent Application Laid-Open No. 2001-35697.
• the antenna In order to suppress an increase in inductance due to the increase in size of the antenna, the antenna It is described that it is possible to reduce the antenna inductance by constructing a planar structure (two-dimensional structure) with a linear conductor that terminates without going around.
• Non-Patent Document 1 Kanagawa AIST Research Report No. 9/2003 77-78
• Patent Document 1 Japanese Patent Laid-Open No. 2004-179658
• Patent Document 2 Japanese Patent Laid-Open No. 2001-35697
• the plasma CDV method is employed so that silicon dots and insulating films can be formed even at relatively low temperatures, and an antenna disposed in the plasma generation chamber is used to improve the utilization efficiency of input power.
• Inductively coupled plasma CVD method is used, and high-density plasma is generated while suppressing abnormal discharge from the internal antenna and damage to the substrate to be processed and silicon dots or insulating film formed on it. Even if a low-inductance antenna is used to form a desired silicon dot or insulating film, there is still a problem.
• a silicon dot insulating film that can be used for a semiconductor device such as a MOS capacitor or a MOS FET has a silicon dot particle size or a silicon dot particle size that is very small, for example, about 10 nm or around that. If the controllability of the diameter and insulating film thickness deteriorates, silicon dots with the required particle diameter and insulating films with the required thickness cannot be formed with good reproducibility. [0019] Therefore, the present invention is relatively low in temperature compared to silicon dot formation by CVD described in, for example, Japanese Patent Application Laid-Open Publication No. 2004-179658.
• the present invention suppresses generation of silicon dot defects and aggregation of silicon dots that may occur at relatively high temperatures, and damage of silicon dots and insulating films due to plasma.
• the silicon dot and the insulating film can be formed with good reproducibility between the substrates by controlling the silicon dot particle size and the insulating film thickness.
• the second problem is to provide a forming method and apparatus.
• the present invention provides the following silicon dot forming method and apparatus.
• the present invention provides the following method and apparatus for forming a substrate with silicon dots and an insulating film.
• first is used to distinguish the plasma generation chamber and antenna for silicon dot formation from the plasma generation chamber and antenna for insulation film formation.
• the plasma generation chamber, antenna, etc. with the word “first” are for silicon dot formation.
• the term “second” is used to distinguish the plasma generation chamber, antenna, etc. related to the formation of the insulating film from the plasma generation chamber, antenna, etc. related to the formation of silicon dots. Indicate that the plasma generation chamber, antenna, etc. with the word “second” are for forming an insulating film!
• the inductively coupled plasma is generated from the silicon dot forming gas supplied to the chamber by applying high frequency power to the first antenna with low inductance installed in the first plasma generating chamber.
• Silicon dots on the substrate placed in the room under In forming the silicon dots do not expose the substrate to the unstable plasma while the plasma generated in the first plasma generation chamber is in an unstable state! And forming a silicon dot on the substrate by allowing the substrate to face the stabilized plasma when the plasma is stabilized.
• a first gas supply device for supplying a gas for forming silicon dots to the first plasma generation chamber; a first antenna having a low inductance installed in the first plasma generation chamber; and a high-frequency power for the first antenna.
• a first high-frequency power application device for generating inductively coupled plasma from the gas supplied and supplied from the first gas supply device to the first plasma generation chamber;
• the silicon dot formation target substrate placed in the first plasma generation chamber is not exposed to the unstable plasma while the plasma in the first plasma generation chamber is in an unstable state.
• a first plasma state grasping device for grasping a state of the plasma generated in the first plasma generation and a plasma state in the first plasma production chamber grasped by the first plasma state grasping device are in an unstable state.
• the substrate is not exposed to the unstable plasma! /, And when the plasma is stabilized, the first plasma state response device is controlled so that the substrate faces the stabilized plasma.
• 1 Silicon dot forming device including a control unit.
• the silicon dots are formed by the silicon dot forming method according to the present invention, and the insulating film is supplied into the chamber by applying high-frequency power to the low-inductance second antenna installed in the second plasma generation chamber.
• Inductively coupled plasma is generated from the insulating film forming gas, and the substrate is placed in the chamber under the inductively coupled plasma.
• An insulating film forming method for forming an insulating film is employed, and when forming an insulating film by the insulating film forming method, the substrate is not used while the plasma generated in the second plasma generating chamber is in an unstable state. Do not expose to stable plasma!
• the substrate When the plasma stabilizes, the substrate is exposed to the stabilized plasma to start the formation of an insulating film on the substrate, and when the insulating film is formed after the formation of silicon dots
• the substrate is communicated from the outside to the second plasma generation chamber from the chamber in which the substrate is located (the first plasma generation chamber or the termination processing chamber when the termination processing chamber described later is used) to the second plasma generation chamber.
• Substrate transfer path substrate transfer path connecting the first and second plasma generation chambers, or when using the termination process chamber described later, the termination process chamber and the second plasma generation chamber are directly connected to each other or the first plasma generation chamber.
• the substrate Connected through When the silicon dot is formed after the insulating film is formed by moving the substrate through the substrate transfer passage, etc., the substrate is connected from the second plasma generation chamber to the first plasma generation chamber, and both chambers are in airtight communication from the outside.
• a method of forming a substrate with silicon dots and an insulating film that is moved through a transfer path (a substrate transfer path that connects the second plasma generation chamber to the first plasma generation chamber directly or through a termination processing chamber described later).
• the second plasma generation chamber The second plasma generation chamber
• a second gas supply device that supplies a gas for forming an insulating film into the second plasma generation chamber; a low-inductance second antenna installed in the second plasma generation chamber; and high-frequency power applied to the second antenna
• a second high-frequency power application device for generating inductively coupled plasma from the gas supplied from the second gas supply device to the second plasma generation chamber
• the substrate placed in the second plasma generation chamber is not exposed to the unstable plasma while the plasma in the second plasma generation chamber is unstable, and the plasma is stabilized.
• a second plasma state handling device for facing the stabilized plasma, a second plasma state grasping device for grasping the state of the plasma generated in the second plasma generation chamber, and When the plasma state in the second plasma generation chamber grasped by the second plasma state grasping device is unstable, the substrate is not exposed to the unstable plasma, and when the plasma is stabilized, the plasma is stabilized.
• a second control unit that controls the second plasma state response device so that the substrate faces the stabilized plasma;
• the first plasma generation chamber and the second plasma generation chamber are formed with a silicon dot and a substrate with an insulating film that are airtightly connected from the outside through a substrate transfer passage for transferring the substrate between the two chambers. apparatus.
• silicon dots are silicon dots having a fine particle diameter of approximately 1 nm to 10 nm.
• the insulating film has a thickness of, for example, about 1 nm to about! OOnm, more preferably about 2 nm to 20 nm.
• the "low-inductance antenna” is a low-inductance antenna compared to a large antenna that circulates around the plasma generation region in the plasma generation chamber. It is a relatively short antenna having an end that faces a region and terminates in a circular manner around the plasma generation region.
• a typical example is a U-shaped antenna.
• the U-shaped antenna literally includes a U-shaped antenna, a gate-shaped or U-shaped antenna, a semicircular arc-shaped antenna, an arc-shaped antenna with a linear portion, and the like. It is.
• the low inductance antennas for example, the inductance L is that of 200 X 10- 9 [H] to 230 X 10- 9 [H] approximately below the frequency of the input RF power to the antenna 13. If 56 MHz, impedance IZI force is about 5 ⁇ or less, further 18 ⁇ to 20 ⁇ or less.
• the "plasma state grasping device” can grasp whether the plasma is in an unstable state or a stable state. Based on (spectral intensity), it is possible to cite whether the plasma is in an unstable state or whether it is in a stable state.
• the internal antenna type inductively coupled plasma CVD method can be used at a relatively low temperature of about 250 ° C or lower, even at a high temperature.
• High-density plasma is suppressed by adopting an internal antenna (first antenna) installed in the first plasma generation chamber that suppresses the occurrence of defects and silicon dot aggregates that may occur, and has a low inductance.
• first antenna installed in the first plasma generation chamber that suppresses the occurrence of defects and silicon dot aggregates that may occur, and has a low inductance.
• the substrate when forming the silicon dots, the substrate is not exposed to the unstable plasma while the plasma generated in the first plasma generation chamber is in an unstable state.
• the substrate When stabilized, the substrate is exposed to the stabilized plasma and silicon dot formation is started on the substrate, so that silicon dots can be formed with good controllability of the silicon dot particle size and good reproducibility between the substrates.
• the silicon dot forming method and the silicon dot forming apparatus are employed, respectively. Therefore, it is possible to suppress the generation of defects and silicon dots that may occur at high temperatures and to form silicon dots with reduced plasma damage. In addition, silicon dots can be formed with good controllability of the silicon dot particle size and good reproducibility between substrates.
• the insulating film is also installed in the second plasma generation chamber at a relatively low temperature of about 250 ° C or lower and with a low inductance by an inductively coupled plasma CVD method using an internal antenna.
• an internal antenna second antenna
• high-density plasma is formed, but the insulating film is formed while suppressing damage to the insulating film caused by the plasma or silicon dots that may be formed earlier. Can do.
• the substrate In forming the insulating film, the substrate is not exposed to the unstable plasma while the plasma generated in the second plasma generation chamber is in an unstable state. When stabilized, the substrate is exposed to the stabilized plasma to start forming an insulating film on the substrate, so that the insulating film can be formed with good controllability of the insulating film thickness and good reproducibility between the substrates.
• the substrate is moved from the chamber in which the substrate is located (the first plasma generation chamber or the termination processing chamber described later when the termination processing chamber is used) to the second plasma. Through the substrate transfer passage that connects both chambers in an airtight manner from the outside to the generation chamber.
• the substrate is moved from the second plasma generation chamber to the first plasma generation chamber through a substrate transfer passage that communicates both chambers in an airtight manner from the outside.
• a substrate with silicon dots and an insulating film can be provided.
• silicon dots are formed in a state where the plasma in the first plasma generation chamber is stabilized.
• An openable / closable shatter device is provided to shield the substrate disposed in the first plasma generation chamber from the plasma generated in the chamber.
• the plasma in the first plasma generation chamber is Until the substrate is stabilized, the substrate is shielded from the plasma by the shatter device and is not exposed to unstable plasma! /
• the shatter device is opened and the source of the stabilized plasma is opened. Then, silicon dot formation may be started on the substrate.
• a substrate retracting device for retracting a substrate disposed in the first plasma generating chamber from the plasma generated in the chamber.
• the unstable state and the stabilized state of the plasma generated in the first plasma generation chamber are, for example, relative to the first plasma generation chamber. It may be grasped by a plasma state grasping device provided.
• the substrate when the plasma state in the first plasma generation chamber grasped by the first plasma state grasping device is in an unstable state, the substrate is made unstable.
• the first plasma state response device is controlled so that the substrate is exposed to the stabilized plasma when the plasma is stabilized.
• the substrate disposed in the first plasma generation chamber is shielded from plasma generated in the plasma generation chamber, or An openable / closable shirter device that faces the plasma, or the substrate disposed in the first plasma generation chamber is retracted from the plasma generated in the first plasma generation chamber, or is moved to a position facing the plasma from the retracted position.
• a substrate retracting device can be employed.
• the first control unit when forming the silicon dots on the substrate, causes the substrate to be moved by the shotta apparatus until the plasma in the first plasma generation chamber is stabilized. It is shielded from plasma and not exposed to unstable plasma, and when the plasma is stabilized, the shirter device is opened so that silicon dots are formed on the substrate under the stabilized plasma. It is sufficient to control the shirt device.
• the first control unit is configured to use the substrate retracting device until the plasma in the first plasma generation chamber is stabilized in forming the silicon dots on the substrate.
• the substrate is retracted so that the substrate retracting device places the substrate at a position facing the stabilized plasma when the plasma is stabilized.
• the device may be controlled.
• a silane-based gas and a hydrogen gas are supplied into the first plasma generation chamber as the silicon dot forming gas, and the inductively coupled plasma is generated from these gases, so that the plasma is unstable. While in the state, do not expose the substrate to the unstable plasma! / When the plasma is stabilized, the substrate is made to face the stabilization plasma and silicon dot formation is started on the substrate. be able to.
• a silicon sputtering target is installed in advance in the first plasma generation chamber, and when forming the silicon dots, a sputtering gas is supplied into the first plasma generation chamber as the silicon dot formation gas. Then, the inductively coupled plasma is generated from the sputtering gas, and the substrate is not exposed to the unstable plasma while the plasma is in an unstable state. When the plasma is stabilized, the plasma is stabilized.
• the substrate is It is also possible to start formation of silicon dots on the substrate by chemical sputtering of the silicon sputter target with the stabilized plasma facing the laser.
• the “silicon sputter target” a commercially available silicon wafer, a target substrate formed with a silicon film, or the like can be employed.
• a silicon sputter target in which a silicon film is formed on a target substrate is, for example, independent of the silicon dot forming apparatus or airtight from the outside to the first plasma generation chamber of the silicon dot forming apparatus (do not touch the outside air!
• a silicon film is formed on the target substrate with a continuous film deposition device (for example, a plasma CVD device such as an inductively coupled plasma CVD device), and the silicon sputter target thus obtained is generated as the first plasma. Bring it into the room and install it.
• a silicon film forming gas is supplied into the first plasma generating chamber, and the gas is turned into plasma by applying high-frequency power to the first antenna. And forming a silicon film on the silicon film formation target member in the first plasma generation chamber, and in forming the silicon dots, sputtering gas is used as the silicon dot formation gas in the first plasma generation chamber.
• the inductively coupled plasma is generated from the sputtering gas and the substrate is not exposed to the unstable plasma while the plasma is in an unstable state.
• the plasma is stabilized.
• the substrate is exposed to the stabilized plasma, and the silicon film is chemically sputtered on the substrate by chemical sputtering of the stabilized plasma.
• the dot formation may be started.
• the “silicon film formation target member in the first plasma generation chamber” is at least one of the inner wall of the first plasma generation chamber and the target substrate that may be installed in the first plasma generation chamber.
• the “silicon film forming gas” may be the same as the “silicon dot forming gas” in terms of the type of gas.
• a typical example of the silicon film forming gas is a gas composed of both a silane-based gas and a hydrogen gas.
• hydrogen gas can be given as a typical example.
• the silicon dot formation apparatus may be configured as follows. That is, for example, the first gas supply device in the silicon dot forming device may supply a silane-based gas and a hydrogen gas as the silicon dot forming gas to the first plasma generation chamber. .
• a silicon sputter target is installed in the first plasma generation chamber, and the first gas supply device is turned into plasma as the silicon dot forming gas, whereby sputtering is performed to chemically sputter the silicon sputter target. It is also possible to supply industrial gas into the first plasma generation chamber! /.
• a silicon film forming gas that forms a silicon film by being converted into plasma is applied to the silicon film formation target member in the first plasma generation chamber.
• termination treatment with oxygen, nitrogen, etc.” means that oxygen or nitrogen is bonded to the surface of the silicon dot, and (Si—O) bond, (Si—N) bond, or (Si—N—N). Say to cause a bond.
• the bonding of oxygen and nitrogen by force and termination treatment functions as if to compensate for defects such as unbonded hands on the surface of the silicon dots before termination treatment.
• a high-quality dot state in which defects are substantially suppressed is formed.
• the silicon dot subjected to such termination treatment is used as a material for an electronic device, the characteristics required for the device are improved.
• the electron mobility in the TFT can be improved and the OFF current can be reduced.
• the reliability of voltage and current characteristics hardly changes even when TFT is used for a long time.
• the silicon dot forming method after silicon dots are formed, high frequency power is applied to at least one termination gas selected from an oxygen-containing gas and a nitrogen-containing gas.
• the surface of the silicon dot may be terminated under the terminated plasma.
• This termination treatment may be performed in the first plasma generation chamber, but after the formation of silicon dots in the first plasma generation chamber, the substrate on which the silicon dots are formed is terminated in a continuous manner with the plasma generation chamber. It is possible to carry it into the processing chamber and carry out the termination processing in the termination processing chamber! /.
• the silicon dot forming apparatus supplies at least one termination gas selected from an oxygen-containing gas and a nitrogen-containing gas into the first plasma generation chamber after the silicon dots are formed. It may further include a gas supply device for termination treatment.
• a termination treatment chamber connected to the first plasma generation chamber so that a substrate on which silicon dots are formed in the first plasma generation chamber can be loaded, and is loaded from the first plasma generation chamber.
• the silicon dot on the substrate is subjected to termination treatment under termination plasma generated by applying high frequency power to at least one kind of termination gas selected from oxygen-containing gas and nitrogen-containing gas. It may further include a termination chamber to be implemented.
• the termination process when the termination process is performed, the termination process may be performed under stabilized gas plasma for termination process, such as by using a plasma state handling apparatus as described above.
• oxygen-containing gas for termination treatment examples include oxygen gas and nitrogen oxide (N 0) gas, and examples of the nitrogen-containing gas include nitrogen gas and ammonia (NH 3) gas.
• the silicon dot forming method and apparatus according to the present invention is suitable for IJ only in the case where only silicon dots are formed in addition to the case where an insulating film or the like is formed on the silicon dots. Monkey.
• the method for forming an insulating film is as follows. (2) The insulating film is formed with the plasma in the plasma generation chamber stabilized.
• An openable / closable shatter device is provided for shielding the substrate disposed in the second plasma generation chamber from the plasma generated in the second plasma generation chamber.
• the second plasma generation chamber is provided.
• the substrate is shielded from the plasma by the shatter device so as not to be exposed to the unstable plasma.
• the shatter device is opened and the stable plasma is opened. In the You can start forming an insulating film on the substrate!
• a substrate evacuation device for evacuating a substrate disposed in the second plasma generation chamber from the plasma generated in the second plasma generation chamber. Until the plasma in the second plasma generation chamber is stabilized, the substrate is withdrawn from the plasma by the substrate withdrawal device and is not exposed to unstable plasma. When the plasma is stabilized, the substrate withdrawal device is used. The substrate may be arranged at a position facing the stabilized plasma to start forming an insulating film on the substrate.
• the unstable state and the stabilized state of the plasma generated in the second plasma generation chamber are determined by, for example, a plasma state grasping device provided for the second plasma generation chamber. I can grasp it.
• the substrate is supported by a substrate holder having a substrate heater, and the substrate is transported from the chamber where the substrate is located to the second plasma generation chamber side when forming the insulating film after forming the silicon dots.
• the substrate is moved through the substrate transfer passage from the second plasma generation chamber to the first plasma generation chamber when the silicon dot is formed after forming the insulating film when the substrate is moved through the passage, the substrate is moved to the substrate holder. It may be moved each time.
• the substrate can be quickly raised to a desired temperature in the next silicon dot formation or insulating film formation, compared to the case where the substrate is removed from the substrate holder and moved.
• a substrate holder having a substrate heating heater and a transport device for the substrate holder are provided, and the substrate holder transport device force S, silicon dot
• the substrate is moved when the substrate is moved from the first plasma generation chamber to the second plasma generation chamber through the substrate transfer path and when the silicon dots are formed after forming the insulating film.
• the substrate may be moved together with the substrate holder.
• the substrate retracting device When the substrate is retracted and placed at the position facing the plasma, the substrate retracting device is configured such that the substrate supported by the substrate holder is retracted together with the substrate holder or placed at a position facing the plasma.
• a silane-based gas and an oxygen gas are introduced into the second plasma generation chamber as the gas for forming the insulating film. Then, the inductively coupled plasma is generated from these gases, and the substrate is not exposed to the unstable plasma while the plasma is in an unstable state.
• the substrate is A case where a silicon oxide insulating film is formed on the substrate by facing the stabilized plasma can be mentioned.
• the second gas supply device of the insulating film forming apparatus uses the silicon oxide insulating film as a gas for forming the insulating film.
• the silane-based gas and oxygen gas for formation may be supplied to the second plasma generation chamber.
• the plasma state in the second plasma generation chamber grasped by the second plasma state grasping device is unstable with respect to the formation of the insulating film.
• the second plasma state response device is controlled so that the substrate is exposed to the stabilized plasma. Includes 2 control units.
• the substrate disposed in the second plasma generation chamber is shielded from or exposed to the plasma generated in the plasma generation chamber.
• a shatter apparatus that can be opened and closed, and a substrate retracting unit that retracts the substrate disposed in the second plasma generating chamber from the plasma generated in the second plasma generating chamber or a position facing the plasma from the retracting position.
• a device can be exemplified.
• the second control unit shields the substrate from the plasma by the shatter device until the plasma in the second plasma generation chamber is stabilized in forming the insulating film on the substrate.
• the plasma is stabilized and the shirter device is opened and completely exposed on the substrate under the stabilized plasma. What is necessary is just to control this shirt apparatus so that edge film formation may be started.
• the second control unit forms the insulating film on the substrate, and the substrate retracting device is used until the plasma in the second plasma generation chamber is stabilized. Evacuated from the plasma and exposed to unstable plasma! When the plasma is stabilized, the substrate evacuation device places the substrate at a position facing the stabilized plasma. What is necessary is just to control an evacuation apparatus.
• FIG. 1 is a view showing an example of an apparatus for forming silicon dots and a substrate with an insulating film according to the present invention.
• FIG. 2 is an explanatory diagram of the shape and dimensions of the antenna.
• FIG. 3A is a view showing the shirt apparatus closed.
• FIG. 3B is a view showing the shirt apparatus shown in FIG. 3A in an opened state.
• FIG. 3C is a view showing another example of the shirt device.
• FIG. 4 is a block diagram showing an example of a control circuit of the shirt device.
• FIG. 5 is a diagram showing a part of the silicon dot forming process by the apparatus of FIG. 1.
• FIG. 6 is a view showing the remaining part of the silicon dot forming process by the apparatus of FIG. 1.
• FIG. 7 is a diagram showing a part of an insulating film forming process by the apparatus of FIG. 1. 8] FIG. 8 is a view showing the remaining part of the insulating film forming process by the apparatus of FIG.
• FIG. 9 is a view showing another example of the apparatus for forming a silicon dot and a substrate with an insulating film according to the present invention.
• FIG. 10 is a block diagram showing an example of a control circuit of the substrate retracting device.
• FIG. 11 is an explanatory diagram of the silicon dot forming process by the apparatus of FIG.
• FIG. 12 is an explanatory diagram of the insulating film forming process by the apparatus of FIG.
• Fig. 13 is a diagram showing the results of an experiment showing that it takes time to stabilize the plasma after the plasma is turned on.
• FIG. 14 is a diagram showing that the silicon oxide film formed by the method according to the present invention has the same current-voltage characteristics as the silicon oxide film formed by the conventional method.
• FIG. 15 is a view showing still another example of the silicon dot and insulating film forming apparatus according to the present invention.
• FIG. 16A shows an example of a semiconductor device using silicon dots.
• FIG. 16B is a diagram showing an example of a semiconductor device using two layers of silicon dots. Explanation of symbols
• Second plasma generation chamber 21 1 Ceiling wall
• Substrate holder support stand 28 Plasma status monitoring device G3 Silane-based gas supply device G4 Oxygen gas supply device 20 Shatter device
• FIG. 1 shows a silicon dot and insulating film forming apparatus A including a silicon dot forming apparatus 1 and an insulating film forming apparatus 2.
• the silicon dot forming apparatus 1 includes a first plasma generation chamber 11, in which two antennas 12 are installed in parallel, and a processing substrate S is supported below the antenna 12.
• a substrate holder 16 is provided.
• the substrate holder 16 includes a heating heater 161 that heats the substrate S to be supported.
• Each antenna 12 has both end portions penetrating the ceiling wall 111 of the plasma generation chamber 11 and projecting outside.
• One end of each of the two antennas 12 protruding to the outside is connected to a bus bar 13, and the bus bar 13 is connected to an output variable high frequency power source 15 through a manching box 14.
• the other end of each of the two antennas 12 protruding to the outside is grounded. Details of the antenna 12 will be described later.
• the plasma generation chamber 11 is connected to a gas supply device G1 for supplying a silane-based gas into the chamber and to a gas supply device G2 for supplying hydrogen gas into the chamber.
• a gas supply device G1 for supplying a silane-based gas into the chamber
• a gas supply device G2 for supplying hydrogen gas into the chamber.
• silane gas monosilane (SiH) gas, disilane (SiH) gas, etc. are used.
• these silane-based gas and hydrogen gas are gas for forming silicon dots
• the gas supply devices G1 and G2 are provided with a first gas supply device for supplying the silicon dot forming gas into the plasma generation chamber 11.
• the plasma generation chamber 11 is also connected to an exhaust device 17 for exhausting from the room and decompressing the room.
• the plasma generation chamber 11 is provided with a plasma state grasping device 18 for grasping the state of inductively coupled plasma formed as described later.
• the insulating film forming apparatus 2 includes a second plasma generation chamber 21, and two antennas 22 are installed in parallel in the chamber 21, and the processing substrate S is supported below the antenna 22.
• Base A plate holder 26 is provided.
• the substrate holder 26 includes a heating heater 261 that heats the substrate S to be supported.
• Each antenna 22 has the same shape and dimensions as the antenna 12, and, like the antenna 12, both end portions penetrate the ceiling wall 211 of the plasma generation chamber 21 and protrude outside the room.
• One end of each antenna 22 projecting to the outside is connected to a bus bar 23, and the bus bar 23 is connected to an output variable high-frequency power source 25 via a manching box 24.
• the other end portion of each antenna 22 protruding to the outside is grounded. Details of the antenna 22 will be described later.
• the plasma generation chamber 21 is connected with a gas supply device G3 for supplying a silane-based gas into the chamber and a gas supply device G4 for supplying oxygen gas into the chamber.
• a gas supply device G3 for supplying a silane-based gas into the chamber
• a gas supply device G4 for supplying oxygen gas into the chamber.
• the silane gas monosilane (SiH) gas, disilane (SiH) gas, etc. are used.
• these silane-based gas and oxygen gas are gases for forming a silicon oxide (SiO 2) film that is an insulating film, and the gas supply devices G 3 and G 4 use the insulating film forming gas into the plasma generation chamber 21. Configure the second gas supply device to supply!
• the plasma generation chamber 21 is also connected to an exhaust device 27 for exhausting from the room and decompressing the room.
• the plasma generation chamber 21 is provided with a plasma state grasping device 28 for grasping the state of inductively coupled plasma formed as described later.
• Each antenna 12 (22) penetrates the ceiling wall 111 (21 1) of the plasma generation chamber 11 (21) in an airtight manner at its straight line portion.
• the height H from the lower end of each antenna 12 (22) in the plasma generation chamber 11 (21) to the chamber ceiling wall 111 (211) is 75 mm.
• the distance between the two antennas 12 and the distance between the two antennas 22 in the plasma generation chamber H! / Slip is 100mm.
• Each antenna 12 (22) is a low-inductance antenna compared to a large antenna that circulates in an annular shape so as to surround the plasma generation region in the plasma generation chamber.
• the antenna 12 (22) is two, as shown, is used in a parallel arrangement, two combined inductance L of the order of 1 50 X 10- 9 [H] to 200 DEG X 10- 9 [H] Yes, when the frequency of the applied high frequency power is 56 MHz, the two impedances together are impedance
• the plasma state grasping devices 18 and 28 have the same configuration, and in this example, whether the plasma is in an unstable state force or in a stabilized state based on the spectral intensity of light emission from the plasma. It can be grasped.
• gas decomposes and various atoms, ions, radicals, etc. appear and light emission occurs.
• the light emission is dispersed, and the gas decomposition is not sufficiently advanced or advanced.
• grasping the spectral intensity of the species indicating that the plasma is still stabilized! /,!, Or in a stabilized state it is determined whether the plasma is in an unstable state. It is possible to grasp whether it is in a state of
• the apparatus for grasping the plasma state include a fiber optical spectrometer (model USB2000, measurement target: luminescent atom, luminescent ion) manufactured by Ocean Optake, Inc., USA, and 45 ° sector manufactured by Hide n, UK.
• a fiber optical spectrometer model USB2000, measurement target: luminescent atom, luminescent ion
• One type high transmittance ion energy analyzer / 4 quadrupole mass spectrometer model HAL EQP500, measurement object: positive ion, negative ion, radical, neutral particle).
• an openable / closable shatter apparatus 10 that can cover the substrate to be processed S supported on the substrate holder 16 from above and shield it from the plasma.
• an openable / closable shirter device 20 that covers the substrate S to be processed supported on the substrate holder 26 from above and shields it from plasma is provided.
• These shatter devices 10, 20 have the same structure, and have a pair of shatter blades si, s2 as shown in Fig. 3A and Fig. 3B.
• Gear train gl The gutter blades sl and s2 can be opened and closed by swinging one of the shatter blades sl through g2 and the other shutter blade s2 through gears IJgl, g3 and g4.
• the shatter blades sl and s2 are closed by swinging so as to approach each other, whereby the substrate S on the substrate holder 16 (26) is shielded from the plasma, and Fig. 3B. As shown, the shatter blades sl and s2 are opened by swinging away from each other, so that the substrate S on the substrate holder 16 (26) can face the plasma.
• the shirt apparatus is not limited to the above.
• a structure having shatter blades sl ′ and s2 ′ that can be opened and closed around the outer axes of the substrate S in the diameter direction of the substrate S may be used.
• the shirter device 10 in the silicon dot forming apparatus 1 is provided with a shirter control unit 41 and formed in the plasma generation chamber 11. While the information that the plasma is in an unstable state is being transmitted from the plasma state grasping device 18 to the control unit 41, the control unit 41 instructs the motor drive circuit 51 to control the shatter blades sl and s2. When information indicating that the plasma is in a closed state is transmitted from the plasma state grasping device 18 to the control unit 41, the control unit 41 instructs the motor drive circuit 51 to perform the shatter blades. Open sl and s2.
• the shotta device 20 in the insulating film forming apparatus is also provided with a shotta control unit 42, and information that the plasma formed in the plasma generation chamber 12 is in an unstable state is obtained from the plasma state grasping device 28. While being transmitted to the control unit 42, the control unit 42 instructs the motor drive circuit 52 to keep the shatter blades sl and s2 closed, and information that the plasma has stabilized is obtained. When transmitted from the plasma state grasping device 28 to the control unit 42, the control unit 42 instructs the motor drive circuit 52 to open the shatter blades sl, s2.
• the plasma generation chamber 11 of the silicon dot forming apparatus 1 and the plasma generation chamber 21 of the insulating film forming apparatus 2 are in airtight communication from the outside through the substrate transfer passage 3.
• An openable / closable gate valve VI is provided between passage 3 and chamber 11, which can shut off chamber 11 from passage 3 in an airtight manner, and chamber 21 is shut off from passage 3 in an airtight manner between passage 3 and chamber 21.
• a gate valve V2 that can be opened and closed is installed.
• a substrate transfer robot 31 is installed in the passage 3.
• the robot 31 includes a substrate transfer arm 311 that can move up and down, rotate, and extend and retract, and the substrate S supported on the substrate holder 16 in the chamber 11 is disposed on the substrate holder 26 in the chamber 21.
• the substrate S supported on the substrate holder 26 in the chamber 21 can be arranged on the substrate holder 16 in the chamber 11.
• a force and substrate transport robot for example, a commercially available substrate transport robot can be used with IJ.
• a silicon dot and insulating film substrate that can be used to form the MOS capacitor and MOSFET structure semiconductor device illustrated in Fig. 16A was formed.
• Example 1 will be described!
• a fiber optical spectrometer model USB2000, manufactured by Ocean Optake, Inc., USA was used.
• a substrate S on which a surface of a P-type semiconductor silicon substrate is thermally oxidized as a target substrate S to form a tunnel silicon oxide film is supported on the substrate holder 16 in the plasma generation chamber 11 and the heater 161 The substrate is heated to 220 ° C.
• the device 18 grasps that the plasma is in an unstable state for a while immediately after the plasma is turned on.
• the shirt device 10 is still closed.
• the shatter control unit 41 receives the information indicating the plasma stabilization state from the device 18 as shown in FIG. And let the substrate S face the plasma. Note that the substrate temperature should reach 220 ° C by this time at the latest. This started the formation of silicon dots on the substrate S Is done.
• silicon dots with an independent particle size of about 5 nm can be obtained for field emission scanning electron microscope (FE-SEM) observation.
• the state of the plasma is grasped by the plasma state grasping device 28. Since the device 28 grasps that the plasma is in an unstable state for a while immediately after the plasma is lit, the shotter control unit 42 is still The shirt device 20 remains closed.
• the shatter control unit 42 receives the information indicating the plasma stabilization state from the device 28 as shown in FIG. And let the substrate S face the plasma. Note that the substrate temperature should reach 220 ° C by this time at the latest. Thereby, formation of an insulating film (control silicon oxide film) on the substrate S is started.
• silicon oxide with a thickness of about 15 nm is measured by ellipsometry. It is the power to obtain a film.
• a substrate that can be used for forming the semiconductor device shown in FIG. 16A is obtained.
• the substrate used for forming the semiconductor device having the silicon dot two-layer structure shown in FIG. After forming the control silicon oxide film as described above, the substrate is transferred again to the plasma generation chamber 11 to form silicon dots, and then the substrate is transferred to the plasma generation chamber 21 to form the silicon oxide film! /.
• a silicon dot and an insulating film in a desired laminated state can be formed by reciprocating the substrate between the plasma generation chambers 11 and 21.
• the silicon dot is formed after the plasma is stabilized, and the force S adopting the shatter apparatus 10, 20 to form the insulating film S
• a substrate retracting device 31 ′ may be employed instead of the shirter device.
• Fig. 9 shows a silicon dot and insulating film forming apparatus A 'including a silicon dot forming apparatus 1' and an insulating film forming apparatus 2 '! /.
• a substrate holder support 100 is provided below the antenna 12 in the plasma generation chamber 11, and a substrate holder 19 having a substrate heater 191 can be placed on the support 100. It ’s like that. Further, a substrate retracting device 31 ′ is provided for the plasma generation chamber 11.
• a substrate holder support 200 is provided below the antenna 22 in the plasma generation chamber 21, and the substrate holder 19 can be placed on the support 200.
• a substrate retracting device 31 ′ common to that for the plasma generation chamber 11 is provided for the plasma generation chamber 21.
• the substrate retracting device 31 ′ is installed in a substrate transfer passage 3 ′ that allows the plasma generation chambers 11 and 21 to communicate with each other in an airtight manner from the outside.
• a gate valve VI is provided between the passage 3 ′ and the plasma generation chamber 11
• a gate valve V2 is provided between the passage 3 ′ and the plasma generation chamber 21. ! /
• the substrate retractor 31 ' can carry the substrate holder that can be moved up and down, rotated, and expanded and contracted.
• An arm 311 ′ is provided, and the substrate holder 19 is moved between the plasma generation chambers 11 and 21 while the substrate S is supported by the arm 311 ′, and the substrate holder 19 is supported by the support base 10 0 in the chamber 11. It can be placed on the support base 200 in the chamber 21 as well.
• Each of the support bases 100 and 200 is provided with a power feeding unit (not shown) for supplying power to the heater 191, and the substrate holder 19 is provided with a power receiving unit (not shown) in contact with the power feeding unit. ing.
• a commercially available substrate transfer robot can be used as the substrate retracting device 31 '.
• a control unit 4 ' is provided for the substrate retracting device 31', and the plasma formed in the plasma generation chamber 11 (21) While the information that the state is unstable is being transmitted from the plasma state grasping device 18 (28) to the control unit 4 ′, the control unit 4 ′ instructs the substrate retracting device drive circuit 5 ′, The base plate holder 19 is retracted from the device 12 'directly under the antenna 12 (22). In this example, retreat to passage 3.
• the control unit 4 ′ instructs the substrate retracting device drive circuit 5 ′ to Place the substrate holder 19 on the support base 100 (200) on 31 '.
• the device A ′ shown in FIG. 9 has substantially the same structure as the device A shown in FIG. 1, and is substantially the same as the parts, parts, etc. in the device A shown in FIG. Parts, parts, etc. are denoted by the same reference numerals as in apparatus A.
• a silicon dot and insulating film-forming substrate forming apparatus A ' Using a silicon dot and insulating film-forming substrate forming apparatus A ', a silicon dot and a substrate with an insulating film that can be used for forming the MOS capacitor and the MOSFET structure semiconductor device illustrated in Fig. 16A were formed.
• Example 2 will be described below.
• the plasma state grasping devices 18 and 28 the above-mentioned fiber optic spectrometer (model U SB2000) manufactured by Ocean Optake was used.
• a substrate to be processed S a substrate S on which a surface of a P-type semiconductor silicon substrate is previously thermally oxidized to form a tunnel silicon oxide film is supported on a substrate holder 19 in a plasma generation chamber 11 and a heater 191 The substrate is heated to 220 ° C.
• the substrate holder 19 While maintaining the inside of the chamber 11 at a silicon dot formation pressure of 0.8 Pa (6 mTorr) by the gas supply and the exhaust device 17, the substrate holder 19 is used by the substrate retractor 31 'as shown in FIG. Is retreated to the passage 3 'together with the substrate S, and in the retracted state of the substrate, high frequency power of 13.56 MHz and 2000 W is applied to the antenna 12 to start generating inductively coupled plasma from the gas.
• the device 18 grasps that the plasma is in an unstable state for a while immediately after the plasma is turned on.
• the control unit 4 ′ still keeps the substrate holder 19 retracted into the passage 3 ′.
• the control unit 4 ′ receives information indicating the plasma stabilization state from the device 18 and puts the holder 19 on the transfer device 31 ′. Place on the support base 100 in the generation chamber 11 and close the gate valve VI. Substrate S is evacuating
• the substrate 19 Since the substrate 19 is still supported by the holder 19 having a large heat capacity, the substrate temperature quickly returns to 220 ° C. Thus, formation of silicon dots on the substrate S is started.
• silicon dots with an independent particle size of about 5 nm can be obtained for field emission scanning electron microscope (FE-SEM) observation.
• the gate valves VI and V2 are opened, and the substrate holder 19 supporting the substrate S on which the silicon dots are formed is transferred from the chamber 11 to the plasma generation chamber 21 of the insulating film forming apparatus 2 ′ by the transfer device 31 ′.
• the gate valve VI is closed and the substrate is heated to 220 ° C.
• the state of the plasma is grasped by the plasma state grasping device 28. Since the device 28 grasps that the plasma is in an unstable state for a while immediately after the plasma is turned on, the control of the transfer device 31 is performed. The part 4 'still has the substrate holder 19 retracted into the passage 3'.
• the control unit 4 ′ receives information indicating the plasma stabilization state from the device 28 and places the holder 19 in the transfer device 31 ′ to the plasma generation chamber. Place it on the support base 200 in 21 and close the gate valve V2. Since the substrate S remains supported by the holder 19 having a large heat capacity during retraction, the substrate temperature quickly returns to 220 ° C. Thus, the formation of the insulating film (control silicon oxide film) on the substrate S is started.
• the substrate used for forming the semiconductor device having the silicon dot two-layer structure shown in FIG. 16B is transferred to the plasma generation chamber 11 again after the control silicon oxide film is formed as described above. Then, transfer the substrate to the plasma generation chamber 21 to form a silicon oxide film!
• a silicon dot and an insulating film in a desired laminated state can be formed by reciprocating the substrate between the plasma generation chambers 11 and 21.
• the silicon dot forming apparatus 1 (1 ') described above and silicon dot formation using the silicon dot forming apparatus may occur at a relatively low temperature and at a high temperature by an inductively coupled plasma CVD method using an internal antenna.
• high-density plasma can be formed, but silicon dots can be formed by suppressing damage to the substrate S and the silicon dots formed on it by the plasma.
• the substrate S is covered with the shirter device 10 and shielded from the plasma, or by the substrate retracting device 31 '.
• the plasma is stabilized, and when the plasma stabilizes, the shatter apparatus 10 is opened and the substrate S is exposed to the stabilized plasma, or the substrate evacuation apparatus 31 ′
• silicon dots can be formed with good controllability of the silicon dot particle size and good reproducibility between the substrates. .
• the silicon dots are relatively low temperature, It is possible to suppress the occurrence of defects that may occur and the gathering of silicon dots, and to form silicon dots with reduced plasma damage. With the force S, silicon dots can be formed with good reproducibility.
• the internal antenna (second antenna) installed in the second plasma generation chamber 21 is also made at a relatively low temperature and has a low inductance by the inductively coupled plasma CVD method of the internal antenna type.
• the internal antenna (second antenna) installed in the second plasma generation chamber 21 is also made at a relatively low temperature and has a low inductance by the inductively coupled plasma CVD method of the internal antenna type.
• the substrate S is shielded from the plasma by the shirter device 20, or by the substrate retracting device 31 '.
• the substrate retracting device 31 By retracting the substrate S from the plasma, the substrate S is not exposed to the unstable plasma, and when the plasma is stabilized, the shirter device 20 is opened and the substrate S is exposed to the stabilized plasma, or the substrate retracting device 31
• the substrate S is placed at the position facing the stabilization plasma, and the formation of the insulating film on the substrate S is started, so the insulating film can be formed with good controllability of the insulating film thickness and reproducibility between the substrates. it can.
• the substrate S is transferred from the plasma generation chamber 11 to the plasma generation chamber 21 or vice versa, it is formed through the substrate transfer passages 3 and 3 'that are airtightly blocked from the outside. It is possible to prevent undesirable impurities in the atmosphere from adhering to and mixing in the formed silicon dots and insulating film, and thus a good silicon dot and insulating film can be obtained.
• FIG. 13 shows the results of measuring the spectral intensity of the hydrogen radical (H a) obtained using the fiber optical spectrometer (model USB2000).
• the horizontal axis represents the elapsed time after the start of plasma lighting
• the vertical axis represents the spectral intensity of the hydrogen radical (H a).
• the substrate S is shielded from the plasma while the plasma is unstable by using the shirter apparatuses 10 and 20, and the plasma When stabilized, the substrate S is exposed to the stabilized plasma, and silicon dot formation and insulating film formation are started.
• an N-type semiconductor silicon substrate is used as the substrate to be processed.
• Insulating film forming apparatus 2 shown in Fig. 1 uses monosilane gas (8.6 ccm) and oxygen gas (30 ccm), maintains the film formation pressure at 0.8 Pa (6 mTorr) and keeps the substrate temperature at 220 ° C.
• Monosilane gas (300ccm) and oxygen gas (l OOOccm) are used in a film-forming apparatus by capacitively coupled plasma CVD using parallel plate electrodes (not shown), and the film-forming pressure is set to 2 ⁇ 7P.
• a silicon oxide film formed on the substrate by applying high frequency power of 13.56 MHz and 1000 W, holding the yarn at a temperature of (20 mTorr) and holding the substrate temperature at 400 ° C.
• Figure 14 shows the results of investigating the current-voltage characteristics of each.
• line L1 represents a film under capacitively coupled plasma
• line L2 represents a film formed by thermal oxidation
• line L3 represents a film formed by insulating film forming apparatus 2.
• the quality is almost the same as that of a conventional silicon oxide film by capacitive coupling plasma CVD or a silicon oxide film obtained by thermal oxidation treatment even at a low temperature as in the present invention. It can be seen that a silicon oxide film exhibiting a dielectric breakdown voltage is obtained.
• the silicon dot forming apparatus 1 in FIG. 1 is used, a P-type semiconductor silicon substrate is used as the substrate to be processed, and monosilane gas (0.2 ccm) and hydrogen gas (30 ccm) are used.
• the dot forming pressure is maintained at 0.8 Pa (6 mTorr), and the input power to the antenna 12 is 13.56 MHz, 2000 W, 250. C, 300. C, 450.
• the following table shows the results obtained by forming silicon dots at each substrate temperature of C and examining the silicon dot particle size at each substrate temperature with a field emission scanning electron microscope (FE—SEM) to determine the particle size variation. Shown in
• an N-type semiconductor silicon substrate is used as the substrate to be processed, and monosilane gas (0.2 ccm) and hydrogen gas (30 ccm) are used, and the silicon dot formation pressure is set to 8 Pa (6 mTorr).
• the input power to the antenna 12 is 13.56MHz, 500W, the substrate temperature is maintained at 220C,
• the following table shows the results obtained by forming silicon oxide films three times each and measuring the film thickness variation of these silicon oxide films by the ebometry method.
• the film thickness reproducibility (small variation) is better than the shotta device 20 and the substrate retracting device compared to the case where the film is formed by exposing the substrate to plasma from the time the plasma is lit without using the shotta device 20. 31 is used to prevent the substrate from being exposed to the plasma in an unstable plasma state, and it is better to form the film after the plasma is stable.
• silicon dots and the insulating film described above a force that employs a silicon substrate having a highly heat-resistant thermal oxide film as a substrate to be processed, for example, a material having a low heat-resistant temperature such as a non-crisp glass substrate Silicon dots and insulating films can be formed on a substrate made of the above materials, and silicon dots and insulating films can be formed on such a substrate as necessary, so that the selection range of the substrate material is wide.
• silicon dots of Example 1 and Example 2 described above a silane-based gas (monosilane gas) and hydrogen gas are supplied into the plasma generation chamber 11 to convert the gas into inductively coupled plasma.
• a silane-based gas monosilane gas
• hydrogen gas hydrogen gas
• silicon dots were formed.
• silicon dots are formed as follows, for example.
• a silicon sputter target T is pasted in advance on, for example, the inner surface of the ceiling wall 111 in the plasma generation chamber 11 to form silicon dots.
• Hydrogen gas is supplied to the substrate, inductively coupled plasma is generated from the gas, and while the plasma is in an unstable state, the substrate S is placed in a state in which the substrate S is not exposed to the unstable plasma in the shatter apparatus 10.
• the shatter apparatus 10 is opened, the substrate S is exposed to the stabilized plasma, and silicon dots are formed on the substrate S by chemical sputtering of the silicon sputtering target T by the stabilized plasma.
• the silicon sputtering target a commercially available silicon wafer or a target substrate on which a silicon film is formed can be employed. [0135] A condition example in this case will be described below.
• Silicon sputter target Single crystal silicon sputter target
• High frequency power applied to antenna 12 60MHz, 4kW
• Silicon dot formation target substrate Silicon wafer covered with thermal oxide film (SiO 2) Substrate temperature: 400 ° C
• silicon dots having a uniform particle size of 10 nm or less could be formed.
• the silicon film forming gas in the case of using the apparatus of FIG. 1, monosilane gas and hydrogen (gas) to generate plasma by applying high-frequency power to the first antenna 12, and into the silicon target member in the chamber 11 (inside the inner wall of the chamber 11 and / or in the chamber 11) under the plasma.
• a silicon film is formed on a target substrate set in advance, and when forming silicon dots, hydrogen gas is supplied into the chamber 11 to generate inductively coupled plasma from the gas, and the plasma becomes unstable.
• the shatter apparatus 10 is closed for a period of time, the substrate S is not exposed to the unstable plasma! /
• the shutter apparatus 10 is opened and the substrate S is exposed to the stabilized plasma. Then, silicon dots are formed on the substrate S by chemical sputtering of the silicon film by the stabilized plasma.
• Room 11 inner wall temperature 80 ° C (heated by a heater installed in the room)
• Room 11 inner wall temperature 80 ° C (heated by a heater installed in the room)
• Target substrate for silicon dot formation Silicon wafer coated with thermal oxide film (SiO 2) Substrate temperature: 430 ° C
• silicon dots with a particle size of 10 nm or less could be formed on average.
• the surface of the silicon dot is preferably terminated with oxygen, nitrogen, or the like.
• the insulating film when the insulating film is formed after the formation of the silicon dots, it is selected from among the oxygen-containing gas and the nitrogen-containing gas.
• the surface of the silicon dot may be terminated under termination plasma generated by applying high-frequency power to at least one kind of termination gas.
• a termination gas may be introduced into 11 and high frequency power is applied to the gas from antenna 12 to generate termination treatment inductively coupled plasma, and the surface of the silicon dot may be terminated under the plasma.
• a termination chamber independent of the silicon dot forming device 1 or 1 ' is prepared, and termination treatment is performed in the termination chamber under the capacitively coupled plasma or inductively coupled plasma of the termination gas. You can carry out the process!
• the substrate on which the silicon dots are formed is placed in the chamber (directly or indirectly via a transfer chamber having an article transfer robot, etc.). ) It may be carried into a terminal treatment chamber provided in series and the termination treatment may be performed in the termination treatment chamber.
• a substrate transfer passage that connects the termination chamber and the plasma generation chamber 21 from the outside is provided, and an insulating film is formed on the silicon dots after termination.
• the insulating film may be formed by carrying the substrate into the second plasma generation chamber 21 from the passage.
• the antenna that applies high-frequency power to the termination gas An antenna for generating
• an oxygen-containing gas or (and) a nitrogen-containing gas is used as the termination gas, and examples of the oxygen-containing gas include oxygen gas and nitrogen oxide (NO) gas. Examples thereof include nitrogen gas and ammonia (NH 3) gas.
• Substrate temperature on which silicon dots are formed 400 ° C
• Oxygen gas introduction amount lOOsccm
• RF power to antenna 12 13. 56MHz, lkW
• Substrate temperature on which silicon dots are formed 400 ° C
• the silicon dot terminated with oxygen or nitrogen can improve the characteristics of an electronic device using the silicon dot.
• the power S can be improved to improve luminance.
• the present invention relates to the formation of micro-sized silicon dots used as electronic device materials, light-emitting materials, and the like, as well as silicon dots formed by overlapping silicon dots and insulating films that can be used in semiconductor devices such as MOS capacitors and MOS FETs, and the like. It can be used to form a substrate with an insulating film.

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