Classifications

• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P32/00—Diffusion of dopants within, into or out of wafers, substrates or parts of devices
  • H10P32/10—Diffusion of dopants within, into or out of semiconductor bodies or layers
  • H10P32/12—Diffusion of dopants within, into or out of semiconductor bodies or layers between a solid phase and a gaseous phase
  • H10P32/1204—Diffusion of dopants within, into or out of semiconductor bodies or layers between a solid phase and a gaseous phase from a plasma phase

Definitions

• the present invention relates to a method and an apparatus for introducing impurities in a process of manufacturing a semiconductor or the like, and an element manufactured by the method.
• a film of an oxide or the like in which atoms constituting the solid substrate are combined with oxygen in the air is formed on the surface of the solid substrate.
• impurities are physically introduced from a film such as an oxide by means of ion implantation or the like.
• energy is given to ions serving as impurities by an electric field or the like, and the surface is irradiated to introduce impurities into the solid substrate.
• a technology for forming a shallow junction has been required with the miniaturization of devices.
• a conventional shallow junction formation technique a low energy ion implantation technique can be cited.
• ions are extracted from the ion source at a somewhat high voltage and then decelerated at a later stage to maintain a somewhat high beam current value and to perform low-energy implantation. ing.
• a shallow impurity layer of several 10 nm, which has been industrially applied to the manufacture of semiconductors.
• Plasma doping is a technique in which plasma containing desired particles is brought into contact with the surface of an object to be processed such as a semiconductor substrate to introduce the desired particles into the surface of the object to be processed.
• the plasma has a low energy of only a few hundred volts, so it is suitable for forming a shallow impurity layer. It has been tell.
• an experiment which has achieved the shallowest P-type junction at present is disclosed in Technical Digest of Symposium on VL SIT technology, Honolulu P. 110 (20000). According to this, the junction depth is 7 nm.
• Gas phase doping using a gas source is also described in IWJ T, p. 19 (200), J. Vac. Sci. Technol. A16, P.1, (19) 98), Silicon Technology No. 39 18 th June, 2002.
• This is a method that can be at atmospheric pressure of hydrogen by heating the semiconductor foundation, to form impurity diffusion layers of the P-type and N-type by supplying B 2 H 6 and PH 3.
• the hydrogen carrier gas has the effect of removing the natural oxide film on the silicon and keeping the clean surface, thereby suppressing the surface segregation of impurities, especially boron.
• a temperature of 600 ° C. or higher is generally required. For example, silicon Tech Noroji one N o.
• the gas phase doping method using a gas source is a technique in which a dopant having no accelerating energy is supplied to a substrate to form an impurity diffusion layer by a surface reaction. It is considered a technology that exceeds the limit.
• these methods generally require a temperature of 600 ° C. or higher to decompose the gas. At this temperature, photoresist cannot be used as a mask material. Therefore CVD- S i 0 2, etc. must be formed and Patanin grayed and there is want Utoyuu problems process of a transistor forming process is increased. Disclosure of the invention
• the method of introducing impurities includes a method of irradiating plasma to the surface of the solid substrate, a method of irradiating gas to the surface of the solid substrate, and a method of irradiating gas to the surface of the solid substrate when introducing a substance to the solid substrate having a film such as an oxide adhered to the surface.
• the film such as the oxide is removed by at least one means selected from the group consisting of a means for immersing the surface in a reducing liquid, and then desired particles are attached or introduced.
• the impurity introducing device includes a means for irradiating plasma to the surface of the solid substrate, a means for irradiating gas to the surface of the solid substrate, and a means for irradiating gas to the surface of the solid substrate when introducing a substance to the solid substrate having a film such as an oxide adhered to the surface.
• the film such as the oxide is removed by at least one means selected from the group consisting of a means for immersing the surface in a reducing liquid, and then desired particles are attached or introduced.
• An impurity introducing element is a means and a means for irradiating plasma to the surface of a solid substrate when introducing a substance to a solid substrate having a film such as an oxide adhered to the surface.
• the film of the oxide or the like is removed as a treatment of the surface of the solid substrate by at least one means selected from the group consisting of a means for irradiating the surface of the solid substrate with a gas and a means for immersing the surface of the solid substrate in a reducing liquid. Afterwards, it is produced by attaching or introducing desired particles.
• FIG. 1 is a sectional view of a main part of a process chamber.
• Figure 2 is a diagram of the boron concentration distribution in the depth direction from the surface.
• FIG. 3 is a diagram showing the surface of a silicon semiconductor substrate.
• FIG. 4 is a diagram showing a state where silicon atoms on the surface are activated.
• FIG. 5 is a diagram showing the contact of diborane gas.
• FIG. 6 is a diagram showing a state in which a layer containing polon atoms is formed on the surface of a silicon semiconductor substrate.
• BEST MODE FOR CARRYING OUT THE INVENTION The impurity introduction method and the impurity introduction device of the present invention are characterized in that, when introducing a substance into a solid substrate having a film such as an oxide adhered to the surface, plasma is applied to the surface of the solid substrate.
• the plasma for irradiating the surface of the solid substrate argon or hydrogen-based plasma or the like is used.
• a hydrogen-based gas is used.
• the reducing liquid is at least one selected from the group consisting of hydrogen fluoride, sodium hydroxide, aqueous ammonia, sulfinic acid, and di (2-ethylhexyl) adipate.
• solid substrates In the means for immersing the surface in a reducing liquid, it is desirable to mechanically rub the surface of the solid substrate when the surface of the solid substrate is immersed in the reducing liquid. This is because the surface film is more easily removed by mechanical friction.
• One method for adhering or introducing desired particles is to contact a gas containing the desired particles with the surface of the solid substrate from which a film such as the oxide has been removed, and adhere or introduce the gas to or near the surface of the solid substrate. is there.
• another method of adhering or introducing desired particles involves irradiating an electromagnetic wave having an energy exceeding the binding energy between hydrogen or a hydroxyl group and a solid substrate atom adhering to the surface of a solid substrate from which a film such as an oxide has been removed. The bond is changed to a non-bonded state according to the above, the attached hydrogen or hydroxyl group is eliminated, and the atoms constituting the solid substrate are exposed to the surface.
• impurities can be easily attached or introduced to or near the surface of the solid substrate.
• the desired particles approach the vicinity of the atoms constituting the solid substrate at low speed, that is, at low energy. This is because low energy particles are more likely to be trapped by activated atoms.
• low-energy particles are Zuma, gas, and particles in the state of ultra-low energy ions. It is not necessary to decompose the gas containing the desired particles at an elevated temperature.
• the temperature of the solid substrate is less than 600 ° C., and impurities can be introduced even at room temperature.
• the energy of the electromagnetic wave to be irradiated is more than 318 kJ / mo1 and less than 666 kJ / o1.
• the energy is more than 425 kJ / mo1 and less than 666 kJZmo1.
• the reason is that the typical value of the bond energy with oxygen atoms on the surface of the solid substrate is 452 kJZmo1, and it is necessary to irradiate electromagnetic waves in an energy range sufficient to remove oxygen. Because it is desirable.
• the method of attaching or introducing desired particles is performed at a temperature of the solid substrate lower than 600 ° C.
• means for irradiating plasma to the surface of a solid substrate when a substance is introduced into a solid substrate having a film such as an oxide on the surface in a phase of ions, plasma, gas, or the like After removing a film such as an oxide as a treatment of the surface of the solid substrate by at least one means selected from the group consisting of irradiating the surface of the solid substrate with a gas and immersing the surface of the solid substrate in a reducing liquid. Attach or introduce desired particles.
• the desired particles in the impurity introduction method of the present invention are attached or introduced from any state of plasma, gas, and ultra-low energy ions.
• At least one device selected from the group consisting of a device for irradiating plasma to the surface of the solid substrate, a device for irradiating gas to the surface of the solid substrate, and a device for immersing the surface of the solid substrate in a reducing liquid At least one device selected from the group consisting of a device for bringing a gas containing desired particles into contact with the surface of the solid substrate and an annealing device for diffusing the adhered or introduced desired particles is used.
• the apparatus for immersing the surface of a solid substrate in a reducing liquid in the impurity introduction method of the present invention includes a mechanism for mechanically rubbing the surface of the solid substrate.
• the apparatus for bringing the gas containing desired particles into contact with the surface of the solid substrate in the method for introducing impurities according to the present invention uses the bonding energy between hydrogen or a hydroxyl group attached to the surface of the solid substrate from which the oxide or other film has been removed and the atoms of the solid substrate. It has a mechanism to irradiate electromagnetic waves with energy exceeding the limit.
• the active element such as the semiconductor, the liquid crystal and the biochip, and the passive element such as the resistance coil and the capacitor of the present invention are manufactured by the above-described impurity introduction method.
• the impurity introducing apparatus of the present invention when introducing a substance into a solid substrate having a film such as an oxide adhered to the surface, means for irradiating plasma to the solid substrate surface and means for irradiating gas to the solid substrate surface as a treatment of the surface of the solid substrate, the film of the oxide or the like is removed by at least one means selected from the group consisting of: and a means for immersing the surface of the solid substrate in a reducing liquid. Then, desired particles are attached or introduced.
• the plasma in the impurity introduction device of the present invention is a plasma containing a rare gas such as argon or hydrogen.
• the gas in the impurity introduction device of the present invention is a gas containing hydrogen.
• the reducing liquid in the impurity introducing device of the present invention is at least one selected from the group consisting of hydrogen fluoride, sodium hydroxide, aqueous ammonia, sulfinic acid, and di-2-ethylhexyl adipate. .
• the surface of the solid substrate is mechanically rubbed when the surface of the solid substrate is immersed in the reducing liquid.
• the method of adhering or introducing the desired particles in the impurity introducing apparatus of the present invention is performed by bringing a gas containing the desired particles into contact with the surface of the solid substrate from which the film of the oxide or the like has been removed, or at or near the surface of the solid substrate. Adhere or introduce particles into
• the method of adhering or introducing desired particles in the impurity introducing device of the present invention is such that the bonding energy between hydrogen or a hydroxyl group adhering to the surface of the solid substrate from which the film such as the oxide is removed and the atom of the solid substrate is exceeded.
• the bond is changed to a non-bonded state, the attached hydrogen or hydroxyl group is eliminated, and the atoms constituting the solid substrate are exposed on the surface, and then the desired particles are brought into contact with the solid substrate.
• the energy of the electromagnetic wave to be irradiated is more than 318 kJZmol and less than 666 kJZmol.
• the energy is more than 425 kJZmo1 and less than 666 kJZmo1.
• the reason is that the typical value of the binding energy with oxygen atoms on the solid substrate surface is 452 kJ / mo1, and it is necessary to irradiate electromagnetic waves in an energy range sufficient to remove oxygen. Because it is desirable.
• the method of adhering or introducing desired particles in the impurity introducing device of the present invention is performed at a temperature of the solid substrate of less than 600 ° C.
• means for irradiating plasma to the surface of the solid substrate when introducing a substance in a phase of ions, plasma, gas, etc. into the solid substrate having a film such as an oxide adhered to the surface thereof Irradiate gas onto solid substrate surface
• the oxide or other film as a treatment of the surface of the solid substrate by at least one means selected from the group consisting of a means for performing the treatment and a means for immersing the surface of the solid substrate in a reducing liquid, the desired particles are adhered or removed.
• Desired particles in the impurity introduction device of the present invention are attached or introduced from any state of plasma, gas, and ultra-low energy ions.
• the impurity introducing device of the present invention at least one device selected from the group consisting of a device for irradiating plasma to the solid substrate surface, a device for irradiating gas to the solid substrate surface, and a device for immersing the solid substrate surface in a reducing liquid.
• the apparatus has at least one device selected from the group consisting of a device for bringing a gas containing desired particles into contact with the surface of a solid substrate and an annealing device for diffusing the adhered or introduced desired particles.
• the apparatus for immersing the surface of a solid substrate in a reducing liquid in the impurity introduction device of the present invention includes a mechanism for mechanically rubbing the surface of the solid substrate.
• the apparatus for bringing the gas containing the desired particles into contact with the surface of the solid substrate in the impurity introducing apparatus of the present invention is a device that binds to the surface of the solid substrate from which a film such as an oxide has been removed. Equipped with a mechanism for irradiating electromagnetic waves with energy exceeding
• the impurity introducing element of the present invention comprises: a means for irradiating plasma to the surface of the solid substrate and a means for irradiating gas to the surface of the solid substrate when introducing a substance into the solid substrate having a film such as an oxide adhered to the surface.
• the above-mentioned plasma when it is manufactured is a plasma containing a rare gas such as argon or hydrogen.
• the above-mentioned gas used when the impurity introducing element is manufactured is a gas containing hydrogen.
• the reducing liquid used in the production thereof is selected from the group consisting of hydrogen fluoride, sodium hydroxide, aqueous ammonia, sulfinic acid, and di-2-ethylhexyl adipate. Is at least one.
• the solid substrate surface is mechanically rubbed when the solid substrate surface is immersed in the reducing liquid by means for immersing the solid substrate surface in the reducing liquid when the element is manufactured. Is done.
• the method for attaching or introducing desired particles in the production of the impurity-introducing device of the present invention is performed by bringing a gas containing the desired particles into contact with the surface of the solid substrate from which the film such as the oxide has been removed. Attached or introduced on or near the surface of solid substrate.
• the method of attaching or introducing desired particles in the production of the impurity-introducing device of the present invention is as follows: hydrogen or a hydroxyl group adhering to the surface of the solid substrate from which the film such as the oxide has been removed; By irradiating an electromagnetic wave with an energy exceeding the binding energy of, the bond is changed to a non-bonded state, the attached hydrogen or hydroxyl group is eliminated, and the atoms constituting the solid substrate are exposed to the surface.
• the desired particles are brought into contact with each other and adhered or introduced on or near the solid substrate surface.
• the energy of the above-mentioned electromagnetic wave applied when it is manufactured is more than 318 kJ / mol and less than 6666 kJ / mo1. More preferably, the energy is more than 425 kJ / m01 and less than 666 kJ / mo1.
• the reason is that the typical value of the binding energy with oxygen atoms on the solid substrate surface is 452 kJ / mo1, and it is necessary to irradiate electromagnetic waves in an energy range sufficient to remove oxygen. Because it is desirable.
• the method for attaching or introducing the desired particles when the impurity introducing element of the present invention is manufactured is performed at a temperature of the solid substrate of less than 600 ° C.
• the impurity introducing element according to the present invention includes a means for irradiating plasma to the surface of the solid substrate when introducing a substance in a phase of ions, plasma, gas or the like into a solid substrate having a film such as an oxide adhered to the surface.
• a treatment of the surface of the solid substrate the film of the oxide or the like is removed by at least one means selected from the group consisting of irradiating the surface of the solid substrate with a gas and immersing the surface of the solid substrate in a reducing liquid. It is produced by attaching or introducing desired particles.
• desired particles when they are manufactured are attached or introduced from any state of plasma, gas and ultra-low energy ions.
• the impurity introducing element of the present invention is at least one selected from the group consisting of a device for irradiating plasma to the surface of the solid substrate, a device for irradiating gas to the surface of the solid substrate, and a device for immersing the surface of the solid substrate in a reducing liquid. It is manufactured by a device having at least a device group, a device for bringing a gas containing desired particles into contact with a surface of a solid substrate, and an annealing device for diffusing adhered or introduced desired particles.
• the device for immersing the surface of the solid substrate in the production thereof in a reducing liquid is provided with a mechanism for mechanically rubbing the surface of the solid substrate.
• an apparatus for bringing a gas containing desired particles into contact with the surface of the solid substrate when the impurity is introduced is formed of hydrogen or hydrogen adhering to the surface of the solid substrate from which a film such as the oxide is removed.
• a mechanism is provided for irradiating electromagnetic waves with energy exceeding the binding energy between the hydroxyl groups and the solid substrate atoms.
• the impurity introducing element of the present invention is at least one selected from the group consisting of a device for irradiating plasma to the surface of the solid substrate, a device for irradiating gas to the surface of the solid substrate, and a device for immersing the surface of the solid substrate in a reducing liquid. At least two or more devices selected from the group consisting of a device, a device for bringing a gas containing desired particles into contact with the surface of a solid substrate, and an annealing device for diffusing adhered or introduced desired particles, or a combination or integration It is manufactured with the device which did. Embodiments of the present invention will be described below.
• FIG. 1 is a sectional view of a main part of a process chamber.
• a high-frequency wave electric signal generated by a high-frequency power supply 1 is supplied to a coil and an antenna 3 via a matching box 2.
• the matching box 2 matches the high-frequency power supply 1 with the coil and the antenna 3.
• the input impedance of the coil and the antenna 3 and the output impedance of the high frequency power supply 1 are matched and matched. In this way, the high frequency wave electric signal generated by the high frequency power supply 1 is efficiently transmitted to the coil and the antenna 3.
• the high-frequency wave electric signal generated by the high-frequency power supply 12 is supplied to the lower electrode 14 via the matching box 11 Is done.
• the matching box 11 matches the high-frequency power supply 12 with the lower electrode 14. That is, the input impedance of the lower electrode 14 and the output impedance of the high-frequency power supply 12 are matched and matched. By doing so, the high frequency wave electric signal generated by the high frequency power supply 12 is efficiently transmitted to the lower electrode 14.
• Argon (Ar) gas from an argon (Ar) gas source is supplied into the chamber while its flow is controlled by the masochist controller 4.
• the inside of the chamber is depressurized by the turbo molecular pump 6 and the dry pump 8, and is controlled to a desired pressure by the conductance valve 7.
• the transfer path is closed to separate the pre-vacuum chamber and the process chamber.
• a gas introduction pipe for argon gas and diporane gas is separately connected to the process chamber.
• This process chamber has a configuration in which the gas flow can be separately controlled by the mass flow controller 5.
• the surface is sputtered by irradiating with argon plasma.
• the flow rate of the argon gas was 50 sccm
• the pressure inside the chamber was 0.7 Pa
• the helicon part was 150 W
• the bias part was 300 W.
• the spa is held for 70 seconds.
• dipolane (B 2 H 6 ) gas is passed through the chamber for 70 seconds.
• the flow rate of dipolane (B 2 H 6 ) gas is 50 sccm
• the pressure inside the chamber is 1.7 Pa.
• the concentration distribution of boron from the surface to the depth direction is measured by low energy SIMS.
• Figure 2 shows the boron concentration distribution from the surface to the depth.
• the horizontal axis shows the depth from the surface of the semiconductor substrate 13 in nanometers (nm), and the vertical axis shows the boron (B) concentration in the number of atoms per cubic centimeter (at oms Zcm 3 ). Indicated by. As shown in Figure 2, it takes only about 5 nm for the boron (B) concentration to drop by four orders of magnitude. If the position where the concentration of boron (B) is 1 ⁇ 10 18 / cm 3 is the position of the junction, the position of the junction is 3 to 4 nm. Thus, an extremely shallow profile is observed. Boron (B) is stably adsorbed at room temperature.
• Injection volume of Poron (B) is about 1. SX l O at om s Zcm 2. From the above, it can be seen that a shallow impurity layer can be formed by irradiating the surface of the semiconductor substrate 13 with argon plasma and then injecting diporane (B 2 H 6 ) gas into the inside of the chamber. Further, since the process is performed at room temperature without heating the semiconductor substrate 13, a simple method without increasing the number of processes for forming a transistor can be realized.
• FIG. 3 is a diagram illustrating the surface of a silicon semiconductor substrate.
• the covalent bond of silicon (S i) is generally terminated with a hydrogen atom (H) 16 or a hydroxyl group (OH) 17.
• the terminal silicon atom (S i) 15 is bonded to three other silicon (S i) atoms, and is also bonded to one hydrogen (H) 16 atom or hydroxyl group (OH) 17 I have.
• FIG. 4 is a diagram illustrating a state in which silicon atoms (S i) on the surface are activated. That is, by irradiating the electromagnetic wave, the hydrogen atom (H) 16 and the hydroxyl group (OH) 17 are separated from the terminal silicon atom (S i) 15 and the hydrogen molecule (H 2 ) 18 and the water ( H 2 0) 1 9
• FIG. 5 shows how dipolane (B 2 H 6 ) is contacted.
• a layer containing boron atoms (B) can be formed on the surface of the semiconductor substrate by, for example, bringing the gas of diporane (B 2 H 6 ) 20 into contact with the terminal silicon (S i) atoms.
• Figure 6 shows how a layer containing boron atoms (B) is formed on the surface of the semiconductor substrate. As shown in Fig. 6, a layer containing boron atoms (B) can be formed on the surface of the semiconductor substrate of silicon (S i).
• the layer of boron atoms attached to the surface is in this example one or two atoms thick.
• a semiconductor substrate made of silicon (Si) is used as an example of a solid substrate
• boron (B) is used as an example of an impurity.
• the desired particles After desorbing (H) or hydroxyl group (OH) and exposing the atoms constituting the solid substrate to the surface, the desired particles are irradiated, so that the impurity layer adhered to the surface of the solid substrate has one atom. To several thicknesses. That is, it is possible to form an impurity layer on the order of angstroms.
• the bond energy of a single bond between silicon (S i) and hydrogen (H) atoms is 318 kJ / mo1.
• the single bond energy between silicon (S i) and oxygen (O) atoms is 452 kJ Zmo1.
• the bond energy of a single bond between silicon (Si) atoms is 222 kJ / mo1. Since the terminal silicon (S i) atom is associated with three other silicon (S i) atoms, it is necessary to dissociate the terminal silicon (S i) atom from the silicon (S i) crystal. Energy of k J Zmo 1 is considered necessary.
• the semiconductor substrate 13 as a solid substrate becomes an impurity-introduced element manufactured by the impurity introducing method or the impurity introducing apparatus of the present invention. That is, the semiconductor substrate 13 which is a solid substrate is made of an active element such as a semiconductor, a liquid crystal, a biochip, or the like, a resistor, a coil, a capacitor, or the like manufactured by the impurity introducing method or the impurity introducing apparatus of the present invention. Become a passive element.
• the impurity introducing method and the impurity introducing apparatus according to the present invention can form a shallow impurity layer more easily.
• the device according to the present invention is manufactured by this impurity introduction method or impurity introduction device, and a shallow impurity layer is formed. According to the present invention, further miniaturization of the device is realized.

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• 2002
  • 2002-09-20 JP JP2002274554A patent/JP2004111776A/ja active Pending
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  • 2003-09-19 WO PCT/JP2003/012001 patent/WO2004027847A1/ja not_active Ceased
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