KR102671466B1 - Method for forming low temperature poly silicon - Google Patents

Abstract

The method for forming low-temperature crystalline silicon according to the present invention includes preparing a substrate in a reaction space, exposing the substrate to a first silicon-containing gas to form a first adsorption layer of the first silicon-containing gas on the surface of the substrate, and forming a first adsorption layer of the first silicon-containing gas on the surface of the substrate. The crystalline silicon layer may be formed by exposing the adsorption layer to a hydrogen-containing plasma gas to form a first adsorption layer as a silicon layer, and forming the first adsorption layer as a silicon layer. Therefore, a silicon layer can be formed on the surface of the substrate at a low temperature, and the silicon layer can be formed up to the lower surface of the fine pattern on the substrate.

Description

Method for forming low temperature crystalline silicon {METHOD FOR FORMING LOW TEMPERATURE POLY SILICON}

The present invention relates to improved methods and devices for forming crystalline silicon on silicon substrates. In particular, the present invention relates to a substrate processing chamber and method for forming polycrystalline silicon with improved uniformity on a patterned internal surface of a semiconductor substrate.

Silicon and silicon-containing films are used in a wide variety of applications in industries such as semiconductor, display, and solar cells. The silicon layer includes polycrystalline silicon (poly-Si) and epitaxial silicon, and the silicon-containing film includes silicon germanium (SiGe), silicon germanium carbide (SiGeC), silicon carbide (SiC), and silicon nitride (SiN).

Silicon formation can vary in crystallinity depending on the reaction temperature. Silicon formed at low reaction temperatures is mostly in an amorphous state. At higher deposition temperatures, a mixture of amorphous silicon and polysilicon or polysilicon alone can be deposited.

In general, thin film transistors containing a polycrystalline silicon layer have the advantage of high electron mobility and the ability to configure CMOS circuits, so they are widely used in switching elements of high-resolution display panels or projection panels that require a large amount of light.

Methods for crystallizing amorphous silicon into polycrystalline silicon include a solid phase crystallization (SPC) method in which the amorphous silicon layer is annealed at a temperature of about 700°C or lower for several to tens of hours, and an excimer laser is applied to the amorphous silicon layer. Eximer laser annealing (ELA) is a method that crystallizes by scanning and locally heating a high temperature for a very short period of time. Metals such as nickel, palladium, gold, and aluminum are brought into contact with or injected into an amorphous silicon layer, and the metal is formed by the metal. Metal induced crystallization (MIC) method utilizes the phenomenon in which a phase change is induced from an amorphous silicon layer to a polycrystalline silicon layer. Silicide generated by the reaction of metal and silicon continues to propagate laterally, sequentially forming amorphous silicon. There is a metal induced lateral crystallization (MILC) method that induces crystallization.

However, the solid-state crystallization method not only requires too long a process time, but also has the problem of easily causing deformation of the substrate due to heat treatment at high temperatures for a long time. The excimer laser crystallization method not only requires an expensive laser device, but also produces protrusions on the polycrystallized surface. Therefore, there is a disadvantage that the interface characteristics between the semiconductor layer and the gate insulating film are poor, and when crystallization is performed using the metal-induced crystallization method or the metal-induced lateral crystallization method, a large amount of the metal catalyst remains in the crystallized polycrystalline silicon layer, reducing the leakage current of the thin film transistor. There is a downside to increasing it.

The present invention is intended to solve the above-described conventional problems, and its technical task is to provide a method of forming a silicon layer to the lower surface of a fine pattern on a substrate at low temperature.

The method of forming crystalline silicon on a substrate according to this embodiment to achieve the above object includes preparing a substrate in a reaction space; exposing the substrate to a first silicon-containing gas to form a first adsorption layer of the first silicon-containing gas on the surface of the substrate; and exposing the first adsorption layer to a hydrogen-containing plasma gas to form the first adsorption layer into a silicon layer, wherein the first silicon-containing gas is an organic silicon source or halo silicon. silicon) source, and steps (b) and (c) are repeated to form a crystalline silicon layer up to a set thickness.

In addition, another method of forming crystalline silicon on a substrate according to this embodiment to achieve the above object includes preparing a substrate in a reaction space; exposing the substrate to a first silicon-containing gas to form a first adsorption layer of the first silicon-containing gas on the surface of the substrate; exposing the first adsorption layer to a second silicon-containing gas to form a second adsorption layer of the second silicon-containing gas on the first adsorption layer; and exposing the second adsorption layer to a hydrogen-containing plasma gas to form the first adsorption layer and the second adsorption layer into a silicon layer, wherein the first silicon-containing gas is an organic silicon source. or a halo silicon source, and the second silicon-containing gas is selected from an inorganic silicon source, and steps (b) to (d) are repeated to form a crystalline silicon layer to a set thickness. You can.

In addition, another method of forming crystalline silicon on a substrate according to this embodiment to achieve the above object includes preparing a substrate in a reaction space; exposing the substrate to a first silicon-containing gas to form a first adsorption layer of the first silicon-containing gas on the surface of the substrate; forming the first adsorption layer into a silicon layer by exposing the first adsorption layer to hydrogen plasma gas; exposing the silicon layer to a second silicon-containing gas to form a silicon layer resulting from the second silicon-containing gas on the silicon layer; and exposing the silicon layer resulting from the second silicon-containing gas to a hydrogen-containing plasma gas to form the silicon layer resulting from the second silicon-containing gas into a silicon layer, wherein the first silicon-containing gas is is selected from an organic silicon source or a halo silicon source, and the second silicon-containing gas is selected from an inorganic silicon source, and steps (b) to (d) are repeated to determine a set thickness. A crystalline silicon layer can be formed up to.

According to the means for solving the above problem, the substrate processing method according to the present invention has the effect of forming a silicon layer on the surface of the substrate at low temperature by treating the silicon-containing gas adsorbed on the substrate with hydrogen plasma.

In addition, the substrate processing method according to the present invention has the effect of forming a silicon layer up to the lower surface of a fine pattern on the substrate by treating the silicon-containing gas adsorbed on the substrate with hydrogen plasma.

1 is a diagram conceptually showing a substrate processing apparatus according to an embodiment of the present invention.
Figure 2 is a flowchart showing the steps of forming a silicon layer on a substrate according to the first embodiment of the present invention.
Figure 3 is a flowchart showing the steps of forming a silicon layer on a substrate according to a second embodiment of the present invention.

The meaning of terms described in this specification should be understood as follows.

Singular expressions should be understood to include plural expressions unless the context clearly defines otherwise, and terms such as “first” and “second” are used to distinguish one element from another element. The scope of rights should not be limited by these terms.

Terms such as “include” or “have” should be understood as not precluding the presence or addition of one or more other features, numbers, steps, operations, components, parts, or combinations thereof.

The term “at least one” should be understood to include all possible combinations from one or more related items. For example, “at least one of the first, second, and third items” means each of the first, second, or third items, as well as two of the first, second, and third items. It means a combination of all items that can be presented from more than one.

The term “on” means not only the case where a component is formed directly on top of another component, but also the case where a third component is interposed between these components.

Hereinafter, preferred embodiments according to the present invention will be described in detail with reference to the drawings.

Referring to FIG. 1, FIG. 1 is a simple conceptual diagram of a substrate processing apparatus according to an embodiment of the present invention. The substrate processing apparatus 1 includes a process chamber 10, a susceptor 20 supporting the substrate W inside the process chamber 10, and a process gas applied to the substrate W placed in the susceptor 20. Process gas injection means 30 supplies the surface of the substrate W to be exposed to the process gas and evacuates the inside of the process chamber 10 or discharges the process gas to the outside of the process chamber 10. It may include an exhaust port 40 and a vacuum pump 50 connected to the exhaust port.

The process chamber 10 includes a chamber lid 12 at a position facing the substrate W and a chamber body 14 coupled to the chamber lid 12, and the chamber lid 12 includes the substrate W ) may be formed with a process gas injection means 30 for supplying the process gas. A process gas supply line may be formed from the outside of the process chamber 10 to supply the process gas into the inside of the process chamber 10, and the process gas supply line may be used to supply the substrate ( Depending on the type and characteristics of the thin film to be formed on W), a gas supply line may be formed through which a selected process gas or a cleaning gas for cleaning the inside of the process chamber 10 is supplied.

The susceptor 20 supports the substrate W introduced into the process chamber 10 and is a heating means for heating the substrate W so that a reaction product can be formed on the substrate W. 60) may be included. The heating means 60 may be formed inside the susceptor 20, may be formed on the lower part of the susceptor 20, or may be formed on the chamber body 14 from the outside of the process chamber 10. The substrate (W) may be heated by passing through .

While the substrate W is placed and supported on the susceptor 20, it may move or rotate within the process chamber 10 by vertical movement or rotation of the susceptor 20.

Process gas can be divided into source gas, reaction gas, purge gas, cleaning gas, etc. required to form a thin film on the substrate (W). In order to form a thin film on the substrate W, a chemical reaction between the source gas and the reaction gas is required, and a purge gas is used to remove or exhaust the source gas or the reaction gas from the inside of the process chamber 10. In order to clean the inside of the process chamber 10, a cleaning gas activated by plasma may be supplied into the process chamber 10.

Figure 2 schematically shows the sequence of forming a silicon layer on the substrate W according to the first embodiment of the present invention. A method of forming a silicon layer on a substrate W of the present invention may include the sequence shown in FIG. 2. The sequence shown in FIG. 2 may be performed in the substrate processing apparatus shown in FIG. 1.

As shown in FIGS. 1 and 2, in order to form a silicon layer on the substrate W, the substrate W is first placed on the susceptor 20 of the substrate processing apparatus 1. The substrate W may include silicon or germanium, may be a glass substrate, an LCD substrate, or a composite semiconductor substrate, and may include a plurality of active elements and/or isolation regions. Additionally, the substrate W may be a patterned substrate, and may include a via or a trench, or a combination thereof.

In step S102, the substrate W may be placed on the susceptor 20 and heated to a process temperature for performing the process.

In step S104, the substrate W is exposed to a first silicon-containing gas. The first silicon-containing gas may be injected onto the substrate W through the process gas injection device 30 of the substrate processing apparatus 1. Exposure may occur while the first silicon-containing gas is adsorbed to the surface of the surface of the substrate W. Due to the characteristics of the adsorption process, the first silicon-containing gas may be formed on the substrate W in units of atomic layers. In addition, the first silicon-containing gas can be absorbed even on the inner surface of the pattern or trench formed on the substrate W.

In step S104, the temperature of the substrate W may be 25°C to 600°C, or 80°C to 450°C. The pressure inside the process chamber can range from 0.1 Torr to several tens of Torr, or it can be lower or higher than this. The temperature of the substrate W may be maintained at the same or similar temperature in subsequent steps, and may be lower than the thermal decomposition temperature of the second silicon-containing gas to which the substrate W is exposed.

The first silicon-containing gas may be selected from an organic silicon source or a halo silicon source.

Organic silicon sources or halo silicon sources have a lower thermal decomposition temperature compared to silane (SiH ₄ ) or disilane (Si ₂ H ₆ ). Additionally, a silicon bond can be formed on the substrate W in a relatively faster time. Additionally, by adsorbing the organic silicon source to the surface of the substrate (W), the energy required to form a silicon bond later can be lowered.

In the first embodiment of the present invention, the first silicon-containing source is specifically tetrakisdimethylaminosilane (Si[N(CH ₃ ) ₂ ] ₄ ; 4DMAS), trisdimethylaminosilane (Si[N(CH ₃ ) ₂ ] ₃ H; 3DMAS), Bistertiarybutylamino silane; SiH ₂ [NH(C ₄ H ₉ )] ₂ ; BTBAS), bis-diethylaminosilane; Si[N(C ₂ H ₅ ) ₂ ] ₂ H ₂ ; diethylaminosilane (DEAS), diisopropylaminosilane (DIPAS), bis-ethylmethylaminosialne (BEMAS), trisdimethylaminosilane ( tris-dimethylaminosialne (TDMAS), tris-isopropylaminosilane (TIPAS), Hexamethyldisilazane (HMDS), Hexamethyldisiloxane (HMDSO), Diisopropylamino silane; It may be an organic silicon source selected from one or a combination of two or more of DIPAS), tetramethyldisiloxane (TMDSO), and tetraethyl orthosilicate (Si(OC ₂ H ₅ ) ₄ ; TEOS). .

In the first embodiment of the present invention, the first silicon-containing source may be a halo silicon source selected from H ₂ SiBr ₂ , H ₂ SiI ₂ , H ₃ SiF, and H ₃ SiBr. In particular, the halo silicon source of the present invention may not contain a chlorine component.

In step S106, the first silicon-containing gas is discharged or purged from the inside of the process chamber 10. In step S106, the process gas injection means 30 stops spraying the first silicon-containing gas and only exhausts the gas, or stops spraying the first silicon-containing gas and supplies a purge gas inside the process chamber 10. The first silicon-containing gas, excluding the gas introduced and adsorbed on the substrate W, may be removed through the exhaust port 40 of the process chamber 10. The purge gas may be an inert or non-reactive gas such as argon (Ar) gas, nitrogen (N ₂ ) gas, or hydrogen (H ₂ ) gas.

In step S108, the substrate W is exposed to a second silicon-containing gas. The second silicon-containing gas may be injected onto the substrate W through the process gas injection device 30 of the substrate processing apparatus 1. The substrate W includes an adsorption layer of the first silicon-containing gas adsorbed on the surface in step S104, so that the adsorption layer of the first silicon-containing gas is exposed to the second silicon-containing gas. Exposure in step S108 may occur while the second silicon-containing gas is adsorbed to the surface of the substrate W. The second silicon-containing gas may be adsorbed on the adsorption layer of the first silicon-containing gas formed on the surface of the substrate (W). Due to the characteristics of the adsorption process, the second silicon-containing gas may be formed on the substrate W in units of atomic layers. Accordingly, an adsorption layer of the first silicon-containing gas and an adsorption layer of the second silicon-containing gas may be stacked on the substrate W.

To this end, the temperature of the substrate W in step S108 may be 25°C to 600°C, or 80°C to 450°C. At the temperature of the substrate (W), the second silicon-containing gas may be a gas that does not easily adsorb to the surface of the substrate (W) when there is no adsorption layer of the first silicon-containing gas.

The energy required for the second silicon-containing gas to be adsorbed to the surface of the substrate W is lowered due to the adsorption layer of the first silicon-containing gas.

Additionally, the adsorption layer of the first silicon-containing gas may act as a seed to form a silicon bond with the adsorption layer of the second silicon-containing gas.

In the first embodiment of the present invention, the second silicon-containing source may be an inorganic silicon source. The inorganic silicon source is SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , SiH ₂ Cl ₂ , SiH ₃ Cl, SiH ₂ Cl _{2 ,} SiHCl ₃ and SiCl ₄ It may be any one selected from among or a combination of two or more.

In step S110, the second silicon-containing gas is discharged or purged from the inside of the process chamber 10. In step S110, the process gas injection means 30 stops spraying the second silicon-containing gas and only exhausts the gas, or stops spraying the second silicon-containing gas and supplies a purge gas inside the process chamber 10. The second silicon-containing gas, excluding the gas introduced and adsorbed on the substrate W, may be removed through the exhaust port 40 of the process chamber 10. The purge gas may be an inert or non-reactive gas such as argon (Ar) gas, nitrogen (N ₂ ) gas, or hydrogen (H ₂ ) gas.

In step S112, the substrate W is exposed to hydrogen-containing plasma gas. The hydrogen-containing plasma gas may be activated by a plasma generator installed inside or outside the substrate processing apparatus 1, or may be formed into a gas containing hydrogen ions and sprayed on the substrate W. there is. The hydrogen-containing plasma reacts with the adsorption layer of the first silicon-containing gas and the second silicon-containing gas adsorbed on the surface of the substrate (W) to form one or two layers on the surface of the substrate (W). A silicon bonding layer can be formed.

The one- or two-layer silicon bonding layer formed on the surface of the substrate W in steps S104 to S108 may have incomplete bonding or may contain atoms or molecules other than silicon. In step S112, one or two layers of silicon bonding layer at the atomic level may be exposed to hydrogen-containing plasma. Hydrogen-containing plasma can complete incomplete bonding of the silicon bonding layer formed on the surface of the substrate W and remove atoms or molecules other than silicon.

In the first embodiment of the present invention, the hydrogen-containing plasma may be hydrogen (H ₂ ) plasma (H-Plasma). The substrate W is exposed to hydrogen plasma, so that the adsorption layer formed on the surface can be formed into a silicon bond or the imperfect silicon bond formed on the surface can be formed into a complete bond.

In the next step, steps S104 to S112 are repeated. This repetition may be performed until the thickness of the silicon layer formed on the substrate W reaches a predetermined thickness.

Therefore, it is possible to form a silicon layer by forming an adsorption layer of silicon-containing gas at a low temperature and exposing it to hydrogen-containing plasma to form silicon bonds at the atomic layer level in one or two layers and repeating this process. In addition, a silicon layer can be formed by exposing each imperfect silicon bond in the atomic layer unit of the first or second layer formed at low temperature to hydrogen-containing plasma, removing defects in the imperfect silicon bond, and repeating the process of forming a complete silicon bond. There will be.

Meanwhile, in the first embodiment, the substrate W may be additionally exposed to nitrogen-containing plasma after step S112. The silicon layer formed on the surface of the substrate W may be exposed to the nitrogen-containing plasma to form a more dense film. The nitrogen-containing plasma may be nitrous oxide (N ₂ O) plasma.

Figure 3 schematically shows the sequence of forming a silicon layer on the substrate W according to the second embodiment of the present invention. The method of forming a silicon layer on the substrate W according to the second embodiment of the present invention may include the sequence shown in FIG. 3. The sequence shown in FIG. 3 may be performed in the substrate processing apparatus shown in FIG. 1.

As shown in FIGS. 1 and 3, in order to form a silicon layer on the substrate W, the substrate W is first placed on the susceptor 20 of the substrate processing apparatus 1. The substrate W may include silicon or germanium, may be a glass substrate, an LCD substrate, or a composite semiconductor substrate, and may include a plurality of active elements and/or isolation regions. Additionally, the substrate W may be a patterned substrate, and may include a via or a trench, or a combination thereof.

In step S202, the substrate W may be placed on the susceptor 20 and heated to a process temperature for performing the process.

In step S204, the substrate W is exposed to a first silicon-containing gas. The first silicon-containing gas may be injected onto the substrate W through the process gas injection device 30 of the substrate processing apparatus 1. Exposure may occur while the first silicon-containing gas is adsorbed to the surface of the surface of the substrate W. Due to the characteristics of the adsorption process, the first silicon-containing gas may be formed on the substrate W in units of atomic layers. In addition, the first silicon-containing gas can be absorbed even on the inner surface of the pattern or trench formed on the substrate W.

In step S204, the temperature of the substrate W may be 25°C to 600°C, or 80°C to 450°C. The pressure inside the process chamber can range from 0.1 Torr to several tens of Torr, or it can be lower or higher than this. The temperature of the substrate W may be maintained at the same or similar temperature in subsequent steps, and may be lower than the thermal decomposition temperature of the second silicon-containing gas to which the substrate W is exposed.

The first silicon-containing gas may be selected from an organic silicon source or a halo silicon source.

Organic silicon sources or halo silicon sources have a lower thermal decomposition temperature compared to silane (SiH ₄ ) or disilane (Si ₂ H ₆ ). Additionally, a silicon bond can be formed on the substrate W in a relatively faster time. Additionally, by adsorbing the organic silicon source to the surface of the substrate (W), the energy required to form a silicon bond later can be lowered.

In the second embodiment of the present invention, the first silicon-containing source is specifically tetrakisdimethylaminosilane (Si[N(CH ₃ ) ₂ ] ₄ ; 4DMAS), trisdimethylaminosilane (Si[N(CH ₃ ) ₂ ] ₃ H; 3DMAS), Bistertiarybutylamino silane; SiH ₂ [NH(C ₄ H ₉ )] ₂ ; BTBAS), bis-diethylaminosilane; Si[N(C ₂ H ₅ ) ₂ ] ₂ H ₂ ; diethylaminosilane (DEAS), diisopropylaminosilane (DIPAS), bis-ethylmethylaminosialne (BEMAS), trisdimethylaminosilane ( tris-dimethylaminosialne (TDMAS), tris-isopropylaminosilane (TIPAS), Hexamethyldisilazane (HMDS), Hexamethyldisiloxane (HMDSO), Diisopropylamino silane; It may be an organic silicon source selected from one or a combination of two or more of DIPAS), tetramethyldisiloxane (TMDSO), and tetraethyl orthosilicate (Si(OC ₂ H ₅ ) ₄ ; TEOS). .

In the second embodiment of the present invention, the first silicon-containing source may be a halo silicon source selected from H ₂ SiBr ₂ , H ₂ SiI ₂ , H ₃ SiF, and H ₃ SiBr. In particular, the halo silicon source of the present invention may not contain a chlorine component.

In step S206, the first silicon-containing gas is discharged or purged from the inside of the process chamber 10. In step S206, the process gas injection means 30 stops spraying the first silicon-containing gas and only exhausts the gas, or stops spraying the first silicon-containing gas and supplies a purge gas inside the process chamber 10. The first silicon-containing gas, excluding the gas introduced and adsorbed on the substrate W, may be removed through the exhaust port 40 of the process chamber 10. The purge gas may be an inert or non-reactive gas such as argon (Ar) gas, nitrogen (N ₂ ) gas, or hydrogen (H ₂ ) gas.

In step S208, the substrate W is first exposed to a hydrogen-containing plasma gas before being exposed to a second silicon-containing source gas. The hydrogen-containing plasma gas may be activated by a plasma generator installed inside or outside the substrate processing apparatus 1, or may be formed into a gas containing hydrogen ions and sprayed on the substrate W. there is. The hydrogen-containing plasma may react with the adsorption layer of the first silicon-containing gas adsorbed on the surface of the substrate (W) to form a one-layer silicon bonding layer on the surface of the substrate (W).

Additionally, hydrogen-containing plasma may cause large crystals of the silicon bonding layer formed on the surface of the substrate W.

In step S210, the substrate W is exposed to a second silicon-containing gas. The second silicon-containing gas may be injected onto the substrate W through the process gas injection device 30 of the substrate processing apparatus 1. The substrate W includes an adsorption layer of the first silicon-containing gas adsorbed on the surface in step S204, so that the adsorption layer of the first silicon-containing gas is exposed to the second silicon-containing gas. Exposure in step S210 may occur while the second silicon-containing gas is adsorbed to the surface of the substrate (W). The second silicon-containing gas may be adsorbed on the adsorption layer of the first silicon-containing gas formed on the surface of the substrate (W). Due to the characteristics of the adsorption process, the second silicon-containing gas may be formed on the substrate W in units of atomic layers. Accordingly, an adsorption layer of the first silicon-containing gas and an adsorption layer of the second silicon-containing gas may be stacked on the substrate W.

To this end, the temperature of the substrate W in step S210 may be 25°C to 600°C, or 80°C to 450°C. At the temperature of the substrate (W), the second silicon-containing gas may be a gas that does not easily adsorb to the surface of the substrate (W) when there is no adsorption layer of the first silicon-containing gas.

The energy required for the second silicon-containing gas to be adsorbed to the surface of the substrate W is lowered due to the adsorption layer of the first silicon-containing gas.

Additionally, the adsorption layer of the first silicon-containing gas may act as a seed to form a silicon bond with the adsorption layer of the second silicon-containing gas.

In a second embodiment of the present invention, the second silicon-containing source may be an inorganic silicon source. The inorganic silicon source may be any one selected from SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , and SiH ₂ Cl ₂ .

In step S212, the second silicon-containing gas is discharged or purged from the inside of the process chamber 10. In step S212, the process gas injection means 30 stops spraying the second silicon-containing gas and only exhausts the gas, or stops spraying the second silicon-containing gas and supplies a purge gas inside the process chamber 10. The second silicon-containing gas, excluding the gas introduced and adsorbed on the substrate W, may be removed through the exhaust port 40 of the process chamber 10. The purge gas may be an inert or non-reactive gas such as argon (Ar) gas, nitrogen (N ₂ ) gas, or hydrogen (H ₂ ) gas.

In step S214, the substrate W is exposed to hydrogen-containing plasma gas. The hydrogen-containing plasma gas may be activated by a plasma generator installed inside or outside the substrate processing apparatus 1, or may be formed into a gas containing hydrogen ions and sprayed on the substrate W. there is. The hydrogen-containing plasma reacts with the adsorption layer of the first silicon-containing gas and the second silicon-containing gas adsorbed on the surface of the substrate (W) to form one or two layers on the surface of the substrate (W). A silicon bonding layer can be formed.

The first or second layer of silicon bonding layer formed on the surface of the substrate W in step S204 or step S210 may have incomplete bonding or may contain atoms or molecules other than silicon. In step S208 or step S214, one or two layers of silicon bonding layer at the atomic level may be exposed to hydrogen-containing plasma. Hydrogen-containing plasma can complete incomplete bonding of the silicon bonding layer formed on the surface of the substrate W and remove atoms or molecules other than silicon.

In the second embodiment of the present invention, steps S204 to S214 are repeated. This repetition may be performed until the thickness of the silicon layer formed on the substrate W reaches a predetermined thickness.

Therefore, it is possible to form a silicon layer by forming an adsorption layer of silicon-containing gas at a low temperature and exposing it to hydrogen-containing plasma to form silicon bonds at the atomic layer level in one or two layers and repeating this process. In addition, a silicon layer can be formed by exposing each imperfect silicon bond in the atomic layer unit of the first or second layer formed at low temperature to hydrogen-containing plasma, removing defects in the imperfect silicon bond, and repeating the process of forming a complete silicon bond. There will be.

Meanwhile, in the second embodiment, the substrate W may be additionally exposed to nitrogen-containing plasma after step S214. The silicon layer formed on the surface of the substrate W may be exposed to the nitrogen-containing plasma to form a more dense film. The nitrogen-containing plasma may be nitrous oxide (N ₂ O) plasma.

Those skilled in the art to which the present invention pertains will understand that the present invention can be implemented in other specific forms without changing its technical idea or essential features. Therefore, the embodiments described above should be understood in all respects as illustrative and not restrictive. The scope of the present invention is indicated by the claims described below rather than the detailed description above, and all changes or modified forms derived from the meaning and scope of the claims and their equivalent concepts should be interpreted as being included in the scope of the present invention. do.

10: Process chamber 12: Chamber lead
14: Chamber body 20: Susceptor
30: supply gas injection means 40: exhaust port
50: vacuum pump 60: heating means

Claims (10)

delete A method of forming crystalline silicon on a substrate, comprising:
(a) preparing a substrate in the reaction space;
(b) exposing the substrate to a first silicon-containing gas to form a first adsorption layer of the first silicon-containing gas on the surface of the substrate;
(c) exposing the first adsorption layer to a second silicon-containing gas to form a second adsorption layer of the second silicon-containing gas on the first adsorption layer; and
(d) exposing the second adsorption layer to a hydrogen-containing plasma gas to form the first adsorption layer and the second adsorption layer as a silicon layer;
Including,
the first silicon-containing gas is selected from an organic silicon source or a halo silicon source,
the second silicon-containing gas is selected from an inorganic silicon source,
A low-temperature crystalline silicon forming method, characterized in that the steps (b) to (d) are repeated to form a crystalline silicon layer to a set thickness. A method of forming crystalline silicon on a substrate, comprising:
(a) preparing a substrate in the reaction space;
(b) exposing the substrate to a first silicon-containing gas to form a first adsorption layer of the first silicon-containing gas on the surface of the substrate;
(c) forming the first adsorption layer into a silicon layer by exposing the first adsorption layer to hydrogen plasma gas;
(d) exposing the silicon layer to a second silicon-containing gas to form a silicon layer resulting from the second silicon-containing gas on the silicon layer; and
(e) exposing the silicon layer resulting from the second silicon-containing gas to a hydrogen-containing plasma gas to form the silicon layer resulting from the second silicon-containing gas into a silicon layer;
Including,
the first silicon-containing gas is selected from an organic silicon source or a halo silicon source,
the second silicon-containing gas is selected from an inorganic silicon source,
A low-temperature crystalline silicon forming method, characterized in that the steps (b) to (e) are repeated to form a crystalline silicon layer to a set thickness. According to claim 2 or 3,
The organic silicon source is tetrakisdimethylaminosilane (4DMAS), trisdimethylaminosilane (3DMAS), Bistershirebutylaminosilane (BTBAS), bisdiethylaminosilane (BDEAS), diethylaminosilane (DEAS), and dia. Isopropylaminosilane (DIPAS), bisethylmethylaminosilane (BEMAS), trisdimethylaminosilane (TDMAS), trisisopropylaminosilane (TIPAS), hexamethyldisilazene (HMDS), hexamethyldisiloxane (HMDSO) ), diisopropylaminosilane (DIPAS), tetramethyldisiloxane (TMDSO), and tetraethylorthosilicate (TEOS), or a combination of two or more. According to claim 2 or 3,
A method of forming low-temperature crystalline silicon, wherein the halo silicon source is any one selected from H ₂ SiBr ₂ , H ₂ SiI ₂ , H ₃ SiF, and H ₃ SiBr. According to claim 2 or 3,
A method of forming low-temperature crystalline silicon, characterized in that the substrate temperature is 600°C or lower. According to claim 2 or 3,
A method of forming low-temperature crystalline silicon, characterized in that the substrate temperature is lower than the thermal decomposition temperature of the inorganic silicon source. According to claim 2 or 3,
The inorganic silicon source is SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , SiH ₂ Cl ₂ , SiH ₃ Cl, SiH ₂ Cl _{2 ,} SiHCl ₃ and SiCl ₄ A method of forming low-temperature crystalline silicon, characterized in that any one selected from the group consisting of one or a combination of two or more. According to claim 2 or 3,
A method of forming low-temperature crystalline silicon, characterized in that it further comprises the step of exposing the silicon layer to a nitrogen-containing plasma gas after the silicon layer forming step. According to clause 9,
A method of forming low-temperature crystalline silicon, characterized in that the nitrogen plasma gas contains N ₂ O.