KR20220095101A - Repeated Cycle Type Substrate Processing Apparatus - Google Patents

Abstract

An objective of the present invention is to provide a cycle repetition type substrate processing apparatus capable of controlling the deposition of a plurality of films in a process of processing a substrate. According to the present invention, the substrate processing apparatus comprises: a chamber for processing a substrate; and a gas supply unit for supplying gas to the chamber. The supply flow rate and supply time of the gas supplied to the chamber by the gas supply unit may be adjusted to control characteristics of a film deposited on the substrate.

Description

Repeated Cycle Type Substrate Processing Apparatus

The present invention relates to a substrate processing apparatus for processing a substrate of a solar cell by an ALD method.

PVD (Physical Vapor Deposition) and CVD (Chemical Vapor Deposition) as film forming technologies for semiconductor devices have limitations in application to the manufacture of nanoscale super-integrated devices due to an increase in the degree of integration of semiconductor devices. Atomic Layer Deposition (ALD) is drawing attention as an essential technology for manufacturing nanoscale semiconductor devices because it enables the deposition of a nanoscale thin film with excellent uniformity even in a three-dimensional structure with a complex shape.

An object of the present invention is to provide a cycle repeatable substrate processing apparatus capable of controlling deposition of a plurality of films in a substrate processing process.

The substrate processing apparatus of the present invention includes a chamber for processing a substrate, and a gas supply unit for supplying a gas to the chamber, and the supply flow rate and supply time of the gas supplied to the chamber are adjusted by the gas supply unit to determine the characteristics of the film deposited on the substrate can be controlled

The perovskite solar cell may include a plurality of deposition films to help diffusion of electrons and holes, and since an electron transport layer and a hole transport layer are provided above and below the perovskite crystalline layer, interfacial layers having different properties are provided up and down can be Accordingly, it may be easy to perform a complex process by controlling the processes of a plurality of deposition films through one software.

In order to form one target deposition film of the ALD method, a source gas corresponding to a precursor, a reactive gas that chemically reacts with the source gas, and a purge gas that removes gas components other than the target deposition film formed by the chemical reaction from the chamber are provided. can

A source gas, a purge gas, a reactance (reaction) gas, and a purge gas are sequentially introduced to form a target atomic layer, which may be referred to as one cycle. By repeatedly performing the one cycle, the thickness of the deposition film can be adjusted. The input amounts of the source gas, the reaction gas, and the purge gas in each cycle may be the same or different.

Furthermore, the entire series of processes for a plurality of different deposition films can be controlled by one software, and the gas supply amount and supply time between each cycle in one deposition film can be controlled, as well as the gas supply amount and supply between cycles between different deposition films. You can also adjust the time. Through this, the interfacial properties of the photoactive layer including the perovskite layer and the various deposition films facing it can be improved, and thus electrons and holes of the perovskite layer are diffused more efficiently, so that the power conversion efficiency of the solar cell can increase

1 schematically shows one embodiment of a perovskite solar cell.
2 schematically shows a substrate processing apparatus of the present invention.
3 is a graph showing the growth per cycle (GPC) according to the supply time of the source gas of the present invention.
4 is a graph showing the growth per cycle (GPC) according to the supply time of the reaction gas of the present invention.
5 illustrates an embodiment of a process cycle of the substrate processing apparatus of the present invention.
6 illustrates a case in which a processing gas is additionally provided in the process cycle of the present invention.
FIG. 7 shows another embodiment of FIG. 6 .
Figure 8 shows that the individual process cycles of each cycle of the process of the present invention are identical.
Figure 9 shows the different individual process cycles of each cycle of the process of the present invention.
10 shows that the cycle period of each cycle of the present invention is the same.
11 shows that the cycle period of each cycle of the present invention is different.
12 shows another embodiment of FIG. 11 .

The substrate processing apparatus 1 of the present invention may be, for example, an atomic layer deposition apparatus, and may be used in various ALD substrate deposition methods. For example, the substrate processing apparatus may relate to a perovskite solar cell.

A solar cell is a means for converting solar energy into electrical energy, and recently, a perbroskite solar cell has been in the spotlight. Perovskite solar cells can have high visible light absorption and a band gap that is ideal for converting light into electricity. Since the cost is lower than that of a conventional silicon-based solar cell, the disadvantages of a silicon solar cell can be compensated.

Perovskite may refer to a crystal structure, and may generally be expressed by the general formula of ABX ₃ . A and B may be cations and X may be anions. In the perovskite, the A atom may be located at each vertex of the cubic unit cell, the M atom may be a body-centered position, and the X atom may be a face-centered position.

The perovskite structure can have a high electron and hole diffusion distance because electrons and holes can be separated by 1 micrometer or more, making it easier to separate electrons and holes compared to a few nanometers in conventional organic solar cells.

The structure of a typical perovskite solar cell may be arranged in the order of a transparent electrode, an electron transport layer, a perovskite layer, a hole transport layer, and a metal electrode. The structure may be positioned between the substrates.

Each of the electron transport layer, the perovskite layer, and the hole transport layer may be provided in plurality with various types of materials. For example, the electron transport layer may be made of a double layer containing tin oxide particles densely and a porous layer containing zinc oxide particles sparsely. Due to this unique structure, if electrons are well transferred, the electrons separated by the perovskite can reach the electrode more efficiently, thereby increasing the efficiency of the solar cell.

When there are a plurality of deposited layers deposited on the substrate, interfacial properties between the deposited layers may be important to the efficiency of the solar cell. Defects in the interface may decrease the electron and hole transfer efficiency, and consequently the efficiency of the solar cell itself. Therefore, it may be important to control the deposition rate of the deposition film of various materials.

The perovskite layer corresponding to the photoactive layer may include a film for activating the movement of electrons and holes up and down the perovskite, and the film may be an oxide film. In order to generate a voltage of a solar cell, the vertical and opposite movements of electrons and holes are required, and the upper and lower layers of perovskite can perform this role. Accordingly, the upper and lower layers of perovskite may be made of different materials.

Therefore, in order to increase the power conversion efficiency of the perovskite solar cell, an upper and lower oxide layer capable of transporting specific perovskite crystalline electrons and holes well may be provided, and the characteristics of the interfacial layer (IFL) are It can be controlled by the input time and amount of the gas input for deposition.

1 shows a schematic configuration of a perovskite solar cell, in which the perovskite solar cell is a transparent layer 1 that can receive energy from the sun, and indium tin oxide (ITO) that can serve as an electrode (2), an oxide layer (IFL) (3), which is a film capable of transporting holes well, a crystalline layer having a perovskite structure (4), and an oxide layer (IFL) (3), a film capable of transporting electrons well ), may include a metal electrode (5).

The transparent layer 1 may be a substrate W, and sunlight passes through the transparent layer 1 to separate electrons and holes of the perovskite layer 4, and the holes pass through the IFL 3 to serve as an anode. It can migrate to the ITO ( 2 ), and electrons can migrate via the IFL ( 3 ) to the metal electrode ( 5 ) serving as a cathode. Holes and electrons separated from the perovskite 4 may move to a load 6 having a relatively low resistance, and convert energy excited by light energy into electrical energy.

As such, the perovskite solar cell may be composed of a plurality of oxide layers in which the perovskite layer 4 and the IFL 3 are various in order to increase the diffusion distance of holes and electrons due to the characteristics of the perovskite. , for this purpose, various gases for depositing a film on the substrate may be provided.

FIG. 2 schematically shows the substrate processing apparatus 1 of the present invention for forming various deposition films as described above on a substrate. The substrate processing apparatus 1 may include a chamber 200 in which a substrate W for processing a deposition film is provided, and a gas supply unit 100 supplying gases necessary for depositing a film in an ALD method. The gas supply unit 100 may include a gas supply source 110 , a flow rate control unit 120 , a valve 130 , and an inlet.

Each gas is provided by the gas supply source 110, the supply amount is adjusted by the flow rate control unit 120, the supply time is adjusted by the valve 130 to be supplied to the chamber 200 along each input pipe. can

The flow control unit may be configured by a massflow controller.

The chamber 200 may include a substrate support 220 supporting the substrate W, and a shower head 210 that provides a gas supplied from the substrate processing apparatus 1 to the space within the chamber 200 .

In general, a source gas may be provided for atomic film deposition, and a reactive gas that chemically reacts with the source gas may be provided. A desired atomic layer may be formed by a chemical reaction between the source gas and the reaction gas, and a purge gas may be provided to remove components remaining after the reaction through the exhaust port 240 in the chamber 200 .

A gas of a chemical species causing a major chemical reaction may vary depending on a film to be deposited. In general, a source gas and a reaction gas have a chemical reaction, and a purge gas and a processing gas are supplied between the processes to form a process of one cycle. A third reaction gas may be provided, and a plurality of other purge gases such as a first purge gas, a second purge gas, and a third purge gas may be prepared, and the processing gas is also the first processing gas and the second processing gas. , a third processing gas, etc. may be provided in plurality. Accordingly, although one source gas, one supply gas, two purge gases, and one process gas are illustrated in FIG. 2 , the same method may be expanded depending on the type of the deposition layer.

Looking at the process, a source gas may be introduced into the chamber 200 from the substrate processing apparatus 1 , and the source gas may be deposited on the substrate W in one layer. In order to prevent stacking of the substrate W by the source gas, the purge gas may be introduced into the chamber 200 after a predetermined time. Since the purge gas should have a low level of chemical reaction with the source gas or the reactant gas, the purge gas may be provided as a component having low reactivity with other chemical species.

After the concentration of the source gas in the chamber 200 is lowered by the input of the purge gas, the reaction gas may be introduced into the chamber 200 . The input reaction gas may have a chemical reaction with a deposition component of the source gas deposited on the substrate W. An atomic layer of the source gas may be replaced with a component generated by a chemical reaction between the source gas and the reactant gas. The newly substituted film component may be a component targeted to be deposited on the substrate (W). When the target layer is deposited, the remaining components used in the remaining reaction may be evacuated from the chamber 200 again by the purge gas.

The above process may be one cycle of forming a desired atomic deposition film. In this way, one atomic deposition layer can be stacked per cycle, and the thickness of the deposition layer can be adjusted to a desired thickness by a user. By repeating the above cycle, the thickness of the deposited film can be increased.

The purge gas may be supplied throughout one cycle, or the supply may be temporarily stopped while the source gas is being introduced, the supply may be temporarily stopped while the reactive gas is being introduced, or the purge gas may be introduced immediately after the source gas is input, or may be introduced immediately after the reactive gas is introduced.

Due to the components remaining after the chemical reaction, the electrical conductivity of the deposited film may be lowered, and the components in the chamber 200 may be corroded, thereby reducing durability. The chamber 200 may include a trap that may be provided to extend in a horizontal direction of the substrate W. Components remaining after the chemical reaction may corrode traps where gases may stay during the process and the exhaust ports 240 for evacuating gases in the chamber 200, so they may need to be removed quickly.

A process gas may be provided to remove components remaining after the chemical reaction. The processing gas may be rapidly combined with components remaining after the reaction, and may be removed from the chamber 200 together with the purge gas injected after the reaction gas is processed on the substrate W.

A process gas for treating components remaining after a main reaction between the source gas and the reaction gas may be added to the purge gas and supplied together, or may be supplied by adding a separate process from the purge gas. In one embodiment, when hydrogen gas is provided as the processing gas to remove chlorine, the gas D may be a purge gas in which hydrogen gas is added or hydrogen gas may be supplied after the purge step of the gas D.

In the case where the processing gas is provided as a separate process, the processing gas may be, for example, gas E. When the processing gas is individually supplied, the processing gas may be supplied to the chamber 200 through the third inlet 234 .

In the case of depositing the film by the ALD method, a specific desired atomic film may be substituted one by one by a chemical reaction between the source gas and the reactive gas, and components remaining after the reaction by the chemical reaction may exist in addition to the substituted film. , By introducing a purge gas after the chemical reaction, the components remaining after the reaction can be removed from the chamber. Before the purge step, a processing gas may be introduced into the chamber in order to effectively remove impurities that prevent the pure and uniform formation of the deposited layer. The processing gas may be inputted separately from the input of the source gas, the reaction gas, and the purge gas, and may be inputted through a heating method separate from other gases.

When the processing gas is converted into plasma by a separate microwave and put into the chamber 200, discharge occurs without an electrode inside the chamber 200, so there is no contamination by the electrodes, so a device for removing foreign substances in the chamber is required Since there is no such thing, the design of the interior of the chamber 200 can be simplified, and the influence of foreign substances on the substrate can be reduced. In addition, since there is no excessive heating process for generating hydrogen radicals inside the chamber 200, damage due to high temperature of the deposition film may be reduced.

Plasma enhanced ALD (PEALD), one of the ALD processes, can shorten the nucleation time by activating a reactive gas using plasma, and it is possible to deposit with good film properties, but a device that gradually decreases in size due to the isotropy of plasma may have relatively poor stair coating properties. Thermal ALD, which is another ALD process, may have poor film properties due to a very long nucleation time and a large grain boundary during thin film formation, but may have superior stair coating properties compared to PEALD.

Therefore, when the deposition film is formed on the substrate by the ALD method, the step coverage ratio of the deposited film can be increased by converting the processing gas into plasma by a separate microwave and supplying it to the chamber either by the PEALD method or the thermal plasma method. .

In the ALD process, the amount of process gas increases as the size of the substrate W increases. This increase in process by-products interferes with the smooth passage of the exhaust path to the exhaust port 240 during the process. In the ALD process, a large amount of gas in the process may be accumulated in the exhaust path and pump system, which may cause malfunction of the pump or the like. In the case of a pump, the exhaust performance deteriorates due to process by-products such as oxide or metal powder accumulating in the pump, and the pump suddenly stops during the process, resulting in an accident where the process system is also shut down. These accidents are frequently experienced in the process mass production line, and many substrates W during the process may be damaged. For this purpose, a trap for collecting process by-products may be provided on the exhaust path, and the trap is installed on the exhaust path to help the smooth exhaust of process by-products to enable stable operation of the vacuum pump, thereby increasing the process yield. can be

In addition to the place where the main process of film formation is performed, chlorine may remain in the trap and the exhaust port 240 corresponding to the path for exhausting the process by-products and cause corrosion. It can be completely exhausted in the process.

Since various gases may be supplied into the chamber 200 from the substrate processing apparatus 1 for film deposition, various gases may be provided in the substrate processing apparatus 1 . Each specific gas may be provided in the gas supply source 110 , and each specific gas may include a source gas, a reaction gas, a purge gas, and a processing gas.

In an embodiment, gas may be introduced into the chamber 200 through three inlets in the substrate processing apparatus 1 .

The gas entering the first inlet 230 may include gas A and gas B, and the gas entering the second inlet 232 may include gas C and gas D. The gas entering the third inlet 234 may be gas E.

Gas A to gas E may all be different types of gas, and some may be the same.

In an embodiment, gas A may be a source gas, gas C may be a reactive gas, gas B and gas D may be purge gases, and gas E may be a process gas.

FIG. 2 may illustrate a case in which a source gas, a reaction gas, a purge gas, or a processing gas are provided as one type.

The purge gas may be supplied to remove components other than the deposited components after the source gas or the reaction gas is added, and the supply of the purge gas is stopped or maintained by the valve 130 while the source gas or the reaction gas is added. may be, and the amount supplied by the flow rate control unit 120 may be adjusted.

An ALD process cycle for one deposited film in which an atomic layer is formed will be described in detail below.

Gas pipes of the source gas and the reaction gas may be introduced into the chamber 200 through different gas pipes so as not to overlap each other in order to prevent contamination between the respective gases. The purge gas may be introduced into the chamber 200 through an inlet separate from the first inlet 230 and the second inlet 232 , and the processing gas may be fed into the chamber 200 through a separate inlet through the third inlet 234 . can be put in

The purge gas may be connected to the source gas tube or the reaction gas tube and may be introduced into the chamber 200 through the same tube through the first inlet 230 or the second inlet 232 . When the purge gas is introduced into the inlet together with the source gas or the reactant gas, the film deposition process is intermittently performed, so that the gas pipe fed in each step may be adjusted by the valve 130 . Therefore, since the gas is not continuously supplied, it may be difficult to maintain a uniform temperature of the gas while the valve 130 is closed during each process. Therefore, the source gas or the reactive gas remaining in the tube of each source gas or reactive gas can be removed with the purge gas, similarly to removing the source gas or the reactive gas in the chamber 200 after the input of each source gas or the reactive gas is finished. have.

In the purge step following each source gas input step or the reaction gas input step, the gases locked by the valve 130 and staying in the source gas tube or the reaction gas tube are also supplied to the chamber 200, but during the purge step, the chamber ( It may be discharged to the exhaust port 240 together with the source gas or the reaction gas in the 200). In this way, when the source gas or the reactive gas is introduced into the chamber 200 through the inlet, the source gas or the reactive gas having a uniform temperature may be introduced.

Looking at the film deposition process step by step, the step of depositing one atomic layer may be formed in five steps.

In the first step, the valve 130 of the tube connected to the source gas may be opened, and the source gas may be introduced into the chamber 200 to be deposited on the substrate W.

In the second step, the valve 130 of the tube connected to the source gas is closed, the purge gas is introduced, and the gas tube connected to the first inlet 230 and the source gas in the chamber 200 can be discharged through the exhaust port 240 . . After the valve 130 of the tube connected to the source gas is closed, the valve 130 of the tube connected to the purge gas (gas B) is opened or closed only while the valve 130 of the tube connected to the source gas is opened during the process, and the remaining process time may still be open.

In the third step, the valve 130 connected to the reaction gas is opened, and the reaction gas may be introduced into the chamber 200 , and the source gas and the reaction gas may undergo a chemical reaction to be substituted with a desired film component.

In the fourth step, a processing gas may be introduced into the chamber 200 to effectively remove components remaining after a chemical reaction to form a specific desired deposition film. The processing gas may be combined with the components remaining after the chemical reaction, and may be discharged to the exhaust port 240 by the purge step of the next step.

The processing gas may be introduced into the chamber 200 by the valve 130 only for a specific period of time to remove components remaining after the reaction after the third step, or may be introduced into the chamber 200 throughout the entire deposition film process.

In the fifth step, the valve 130 of the pipe connected to the reaction gas is closed, and the purge gas is introduced to discharge the gas of the gas pipe connected to the second inlet 232 and the reactive gas in the chamber 200 to the exhaust port 240 . can After the valve 130 of the tube connected to the reaction gas is closed, the valve 130 of the tube connected to the purge gas (gas D) is opened or closed only while the valve 130 of the tube connected to the reaction gas is opened during the process, and the remaining process time may still be open.

The fourth and fifth steps may be performed separately or simultaneously. A uniform deposition film process of one cycle may be completed through the first to fifth steps. Since the fourth step is a process for effectively removing the remaining components after the main chemical reaction, if the radical removal of the process gas after several depositions is formed in process design, the fourth step may be intermittently performed. For example, after performing the first to third steps, the fifth step can be entered immediately, and this is performed several times in one cycle so that the main chemical accumulated in the chamber 200 is accumulated after the deposition film is accumulated by the number of times of the one cycle. The components remaining after the reaction may be removed by the fourth step.

After the source gas is input, the source gas that has not been deposited is removed with a purge gas, and a reaction gas is added to chemically react with the deposited source gas layer to replace the target film, and a purge gas to remove components other than the substituted film is input This may be one cycle for the formation of one specific target atomic layer. By repeating this one process cycle, a deposited film having a desired thickness can be formed. In the case of repeating the above cycle, the film may be formed by repeating the supply amount and supply time of the input gas in the same manner, or the characteristics of the film may be adjusted by varying the supply amount and the supply time of the input gas.

In order to effectively help the diffusion of electrons and holes in the interface layer, it is necessary to control the properties of the deposition film. For this purpose, additional cost is incurred in design when a different type of gas is added to control, but in the case of controlling the characteristics of the film by controlling the supply amount and supply time with the same precursor, that is, the source gas and the reaction gas, there is no major change in the process A desired deposition film can be formed quickly.

As an application example of FIG. 2 , a plurality of source gases, a plurality of reactive gases, and a plurality of purge gases are illustrated for forming a plurality of deposition films. For example, the source gas 1 may be tetrakis(dimethylamino)tin (TDMASn) which is a precursor of Sn, the source gas 2 may be DIPAS (Diisoprophylamino Silane) which is a precursor of Si, and the source gas 3 can be bis(dimethylamino-2-methyl-2-butoxy)nickel(II) [Ni(dmamb) ₂ ]. The reactive gas 1 may be H ₂ 0, the reactive gas 2 may be O ₂ , and the reactive gas 3 may be O ₃ . The purge gas 1 may be NF ₃ , the purge gas 2 may be Ar, and the purge gas 3 may be PN ₂ (purified nitrogen).

For example, the source gas 1 and the reactive gas 1 may chemically react to form a desired specific deposition film, and the purge gas 1 may exhaust the remaining components after the chemical reaction from the chamber to the exhaust port. Although the purge gas fixed to each source gas and the reaction gas is provided in FIG. 2 , a purge gas that can be more effectively combined and exhausted may be selectively designed according to components of the source gas and the reaction gas. Accordingly, through the design, at least one of the source gases, at least one of the reactive gases, and at least one of the purge gases can be controlled through the flow rate control unit 120 and the valve 130 and supplied into the chamber 200 . .

By applying FIG. 2 , the entire process of forming a plurality of deposition films can be controlled by software (S/W). When a plurality of desired deposition films are formed by each of the source gas, the reaction gas, and the purge gas, the process of forming each deposition film can be repeatedly performed through software, and the flow rate is controlled by the command of the software within each deposition film process. The supply amount of each gas in the unit 120 can be adjusted, and the supply time can be adjusted by controlling the opening and closing of the valve 130 by a command of the software.

If the entire straight process of forming the plurality of deposition layers is performed as a full loop, a partial process of supplying each gas may be set as a sub-loop. Thus, by the software, each sub-loop can control the supply flow rate and supply time of each gas. For example, the regulated gas of the supply flow rate may include a source gas, a reactant gas, a purge gas, and a process gas. In order to form a specific deposition film, a layer of source gas is laid, a first purge gas is introduced to remove the source gas from the chamber 200, and a reactive gas is introduced to chemically react with the layer of the source gas. A substituted single layer can be formed. By introducing the second purge gas again, the reaction gas and components remaining after the chemical reaction may be removed from the chamber 200 . The above process may be referred to as one basic cycle for forming an ALD deposition film.

In order to effectively remove the components remaining after the chemical reaction, a processing gas may be introduced. The processing gas may be added to the first purge gas or the second purge gas to be introduced into the chamber 200, may be supplied to the chamber throughout one cycle of the ALD process, and may be supplied to the chamber before or after the second purge gas is supplied. 200) can be supplied.

Each of the gases may form a sub-loop, and between the first process cycle and the second process cycle, that is, between each process cycle, by adjusting the supply flow rate and supply time of each gas, the lower layer and the upper layer of the layer to be deposited characteristics can be adjusted.

For example, referring to FIGS. 3 and 4 , a change in the thickness of a deposited film according to the passage of time of a source gas and a reactive gas may exhibit different characteristics depending on the type of each gas. The total amount of input gas may be calculated as the product of the supply time and the supply flow rate, unless the supply flow rate is given as an abrupt variable with time. However, even with the same total amount of gas, films having different characteristics may be formed depending on the selection of the supply time and the supply flow rate. For example, a process in which a supply time is long and a supply flow rate is small and a process in which a supply time is long and a supply flow rate is the same with the same total amount and a process in which a supply time is short and a large flow rate is supplied at once may have different characteristics of the deposited film. The supply time may be proportional to the opening/closing time of the valve, and the supply flow rate may be proportional to the pressure of a gas pipe that introduces gas into the chamber 200 .

For this reason, the properties of the upper and lower layers in the same deposition layer may be different even if other gas components are not introduced into the process. In the perovskite solar cell, since deposition film layers such as a plurality of oxide layers can be formed on the upper and lower portions of the perovskite layer, the same deposited film can face the oxide film layers having different characteristics vertically, and thus the same deposited film However, it may be necessary for the upper and lower films to have different interfacial properties. Accordingly, the upper and lower interfaces of the deposited film can be created with desired characteristics by using a sub-loop capable of controlling the supply flow rate and supply time of each individual gas in the entire process.

5 to 7 are diagrams illustrating a process of forming a deposition film as a supply flow rate according to time.

5 shows a general, source gas is discharged from the chamber 200 by the first purge gas after one layer of the source gas is formed, and a reactive gas is introduced and chemically substituted after reaction with the source gas to form a component deposition film of a target deposition film Thereafter, it may represent a one-cycle process in which components remaining after reaction with the supplied supply gas are removed from the chamber 200 by the second purge gas. 6 and 7 may illustrate that a processing gas is additionally provided in order to effectively remove components remaining after the reaction in the general ALD deposition film formation process of FIG. 5 from the chamber 200 . 6 is a view illustrating a first purge gas or after a first purge gas is purged with a purge gas after a reactive gas is introduced A process in which the second purge gas is removed may be added to one cycle of FIG. 5 . FIG. 7 may illustrate another embodiment in which a supply time for individually supplying the processing gas is different from that of the embodiment of FIG. 5 . 7A illustrates a case in which the processing gas is supplied immediately after the reaction gas is supplied, and the processing gas is sufficiently removed by the second purge gas after supplying the processing gas due to the purge. 7B illustrates a case in which the processing gas is continuously supplied throughout each cycle, rather than only in a partial section of each cycle.

The first cycle 10 includes a first process 11 of supplying a source gas, a second process 12 of supplying a first purge gas or a second purge gas, and a second process of supplying a reactive gas to replace the source gas layer. The third process 13 may include a fourth process 14 of removing components other than the substituted target deposition layer through the first purge gas or the second purge gas. The first process 11 may essentially include the source gas, the second process 12 may essentially include the first purge gas, and the third process 13 may include essentially the reactant gas. Also, the fourth process 14 may essentially include the second purge gas.

Since one target atomic layer may be formed through the first cycle 10 , another same atomic layer as the first cycle 10 may be formed when the same process is performed in the second cycle 20 . Accordingly, if the first cycle 10 is repeated a plurality of times, a deposition film having a plurality of the same atomic layer may be formed.

In order to have different interface characteristics between the upper and lower portions of the deposited film formed due to the multi-cycle, the supply time and supply flow rate of each sub-process of the first cycle 10 and the second cycle 20 may be adjusted. For example, referring to FIG. 5 , the amount of the second purge gas in the first process 21 of the second cycle may be greater than the supply flow rate of the second gas supplied in the first process 11 of the first cycle. In addition, although the first purge gas is supplied in the third process 13 of the first cycle, the first purge gas may not be supplied in the third process 23 of the second cycle. In this way, the supply time and the supply flow rate of the purge gas may be variously adjusted as needed, and whether supply or not may be adjusted according to circumstances. Similarly, the source gas, the reaction gas, or the processing gas of the first cycle 10 and the second cycle 20 may have different growth per cycle (GPC) of a specific portion of the deposited film by varying the supply time and supply flow rate. and the properties of the interface can be improved according to the purpose.

8 to 9 , each cycle includes a first process 11 in which a source gas is supplied, a second process 12 in which a purge gas is supplied, a third process 13 in which a reaction gas is supplied, and a purge process. A fourth process 14 in which gas is supplied may be included. A second cycle is provided after the first cycle, and the cycle C1 of the first cycle may be the same as or different from the cycle C2 of the second cycle.

The period C1 of the first cycle and the period C2 of the second cycle may be the same, and the individual process periods T1, T2, T3, T4 of each cycle may be the same or different for each cycle. 8 shows a case where the individual process cycle of each cycle is the same for each cycle, and FIG. 9 shows a case where the individual process cycle of each cycle is different for each cycle.

10 to 12 may illustrate a period C1 of the first cycle and a period C2 of the second cycle. By adjusting the cycle of each cycle, it is possible to control the interface characteristics of the upper and lower portions of the targeted deposition film. 10 illustrates a case in which C1 and C2 are the same, and FIG. 11 may indicate that C1 and C2 are different, but individual C1 and C2 are the same. 12 may show that C1 and C2 are also different, and that individual C1 and C2 are also different for each cycle. A user can set a sub-loop by specifying the cycle and flow rate of an individual process, or set a sub-loop for each cycle, or set a sub-loop by combining multiple cycles. For example, a user may capture a sub-loop by adding C1 and C2 having different cycles, and in this case, a specific portion of the deposited film may have a specific interface characteristic targeted by repeatedly performing the sub-loop. In this way, it is possible to control the interface characteristics of the upper and lower surfaces of the deposition film facing the oxide film layer having different characteristics on the upper and lower portions of the perovskite layer.

An embodiment of the present invention will be described once again.

A source gas, a purge gas, a reactive gas, and a purge gas are sequentially sprayed into the chamber by the gas supply unit to form a first cycle, and the same second cycle as the first cycle may be repeated.

A source gas and a reactive gas for film deposition are provided on the substrate, and the gas supply unit injects a first purge gas and a second purge gas for exhausting the source gas or the reactive gas, the source gas, the first purge gas, the reactive gas, and A second purge gas may be sequentially injected into the chamber to form a first cycle, and a second cycle in which at least one different flow rate or supply time of each gas of the first cycle may be performed.

A process gas that is combined with a process by-product generated during the processing of the substrate and exhausted together with the process by-product from the chamber is provided, and the gas supply unit supplies the process gas after a reaction gas supply time or after a second purge gas supply time It may be introduced or continuously supplied over the total time including the supply time of the source gas, the supply time of the reaction gas, and the supply time of the purge gas.

A source gas, a purge gas, a reactive gas, and a purge gas are sequentially injected into the chamber by the gas supply unit to form a first cycle, a second cycle is performed after the first cycle, and the injection flow rate of the purge gas in the second cycle It may be set differently from this first cycle. In the second cycle, a time period in which the injection flow rate of the purge gas is set to be different from that of the first cycle may coincide with the injection period of the source gas or coincide with the injection period of the reaction gas.

source gas. The purge gas, the reaction gas, and the purge gas form a first cycle in which the supply or supply is stopped sequentially, and in the first cycle, the gas supply unit supplies each gas in an intermittent mode or a continuous mode, and the duration of the first cycle is It is defined as a first cycle period, and the continuous mode is a mode in which the purge gas is continuously supplied regardless of the supply period of the source gas and the reaction gas, and the intermittent mode is the source gas supply time point, the source gas supply end point, and the reaction It may be a mode in which the purge gas is supplied or stopped in synchronization with at least one of a gas supply time point and a reactive gas supply end point. A second cycle is performed after the first cycle, and a time point at which a continuous mode or an intermittent mode is selected in the first cycle may be different from a time point at which a continuous mode or an intermittent mode is selected in the second cycle.

In the continuous mode, the first continuous mode is a mode in which the supply flow rate of the continuously injected purge gas is constant, and the second continuous mode in which the supply flow rate of the continuously injected purge gas is partially increased during the supply time of the source gas or the supply time of the reaction gas mode, a third continuous mode in which the supply flow rate of the continuously injected purge gas is partially reduced at the supply time of the source gas or the supply time of the reaction gas may be included.

The first process in which the source gas is injected, the second process in which the purge gas is injected, the third process in which the reaction gas is supplied, and the fourth process in which the purge gas is injected are sequentially performed to form a first cycle, and the first cycle is performed. Thereafter, a second cycle is performed, and at least one process cycle of each process of the first cycle and at least one process cycle of each process of the second cycle may be different.

By controlling the opening and closing of the flow rate control unit 120, the supply flow rate of gas for each cycle or the supply flow rate of gas for each process within a specific cycle is adjusted, and by controlling the opening and closing of the valve 130, the supply time of gas for each cycle Alternatively, the gas supply time for each process may be adjusted within a specific cycle.

1... Transparent layer 2... ITO (Indium Tin Oxide)
3... InterFacial Layer (IFL) 4... Perovskite Layer
5... metal electrode 6... load
10... 1st cycle 11... 1st process of 1st cycle
12... 2nd process of 1st cycle 13... 3rd process of 1st cycle
14... 4th process of 1st cycle 15... 5th process of 1st cycle
20... 2nd cycle 21... 1st process of 2nd cycle
22... Second process in second cycle 23... Third process in second cycle
24... 4th process of 2nd cycle 25... 5th process of 2nd cycle
100... gas supply
110... gas supply 120... flow control
130... valve 200... chamber
210... shower head 220... substrate support
230... first inlet 232... second inlet
234... 3rd inlet 240... Outlet
W... substrate T1... individual process cycles
C1...1st cycle period C2...2nd cycle period

Claims (8)

In the method of manufacturing a perovskite solar cell comprising a perovskite layer, an interfacial layer (IFL), a transparent layer, a metal electrode,
The manufacturing method includes a cycle process of supplying at least one gas of a source gas, a purge gas, and a reaction gas,
The cycle process includes a first cycle process and a second cycle process performed after the first cycle process,
The end time of the first cycle process and the start time of the second cycle process coincide,
The interfacial layer (IFL) is formed by the first cycle process and the second cycle process,
The first cycle process is
a first step of supplying the source gas and a second purge gas;
a second step of supplying the first purge gas and the second purge gas;
a third step of supplying the first purge gas and the reaction gas; and
A fourth step of supplying the first and second purge gases,
The second cycle process is
a first step of supplying the source gas and the second purge gas;
a second step of supplying the first purge gas and the second purge gas;
a third step of supplying the reaction gas; and
A fourth step of supplying the first and second purge gases,
In the first step of each of the first and second cycle processes, the flow rates of the supplied second purge gas are different from each other,
In the third step of each of the first and second cycle processes, the flow rates of the first purge gas supplied are different from each other,
In the first and second cycle processes, the total time of the supplied first purge gas and the total flow rate of the supplied second purge gas are different from each other.
According to claim 1,
The first cycle process further includes a fifth step of supplying the first and second purge gases and a process gas,
The second cycle process is a method of manufacturing a perovskite solar cell further comprising a fifth step of supplying the processing gas.
3. The method of claim 1 or 2,
The interfacial layer (IFL) is a perovsky including a first interfacial layer (IFL) disposed between the transparent electrode layer and the crystalline layer and a second interfacial layer (IFL) disposed between the crystalline layer and the metal electrode A method of manufacturing a solar cell.
4. The method of claim 3,
An upper surface of the first interface layer facing the transparent electrode layer is a method of manufacturing a perovskite solar cell having different interface characteristics from a lower surface of the first interface layer facing the crystalline layer.
4. The method of claim 3,
The upper surface of the second interface layer facing the crystalline layer is a method of manufacturing a perovskite solar cell having different interface characteristics from the lower surface of the second interface layer facing the metal electrode.
In the method of manufacturing a perovskite solar cell comprising a perovskite layer, an interfacial layer (IFL), a transparent layer, a metal electrode,
The manufacturing method includes a cycle process of supplying at least one gas of a source gas, a purge gas, and a reaction gas,
The cycle process includes a first cycle process and a second cycle process performed after the first cycle process,
The end time of the first cycle process and the start time of the second cycle process are
match, The same gas as the gas supplied in the first cycle process is continuously supplied or stopped in the second cycle process,
A supply flow rate of each gas or a supply time of each gas in the first cycle process is different from a supply flow rate of each gas or a supply time of each gas in the second cycle process,
characteristics of the first film formed in the first cycle process and the second film formed in the second cycle process are different;
The first film and the second film form the interfacial layer (IFL) as a continuous stacked film,
A method of manufacturing a perovskite solar cell in which the interfacial layer (IFL) is formed by the first cycle process and the second cycle process.
7. The method of claim 6,
The purge gas includes a first purge gas and a second purge gas,
The first cycle process supplies each gas in an intermittent mode or a continuous mode,
The continuous mode is a mode in which the first purge gas or the second purge gas is continuously supplied regardless of a supply period of the source gas and the reaction gas,
In the intermittent mode, the first purge gas or the second purge gas is supplied in synchronization with at least one of a supply time point of the source gas, a supply end point of the source gas, a supply time of the reaction gas, and a supply end point of the reaction gas. or the aborted mode,
A second cycle process is performed after the first cycle process,
A time point at which the continuous mode or intermittent mode is selected in the first cycle process and a time point at which the continuous mode or intermittent mode is selected in the second cycle process are different from each other.
a chamber for processing a substrate and a gas supply unit for supplying a gas to the chamber; Manufacturing a perovskite solar cell with a substrate processing apparatus comprising a,
A supply flow rate and supply time of the gas supplied to the chamber are adjusted by the gas supply unit to control the characteristics of the film deposited on the substrate,
The gas supply unit injects at least one of a source gas and a reactive gas for film deposition on the substrate, a first purge gas for exhausting the source gas or the reactive gas, and a second purge gas,
The source gas, the first purge gas, the reaction gas, and the second purge gas are sequentially sprayed into the chamber to form a first cycle process,
A second cycle process having a supply flow rate of each gas or a supply time of each gas different from the supply flow rate or supply time of each gas of the first cycle process is performed,
The source gas, the first purge gas, the reactive gas, and the second purge gas injected in the second cycle process include the source gas, the first purge gas, the reactive gas, and the second purge gas injected in the first cycle process; same,
The properties of the first film formed in the first cycle process and the second film formed in the second cycle process are different,
The substrate is used in a perovskite solar cell,
A first interfacial layer, a perovskite layer, and a second interfacial layer are sequentially formed on the substrate,
The genital first interfacial layer and the second interfacial layer include a plurality of oxide layers,
The plurality of oxide layers include a first oxide layer and a second oxide layer,
When electrons and holes of the perovskite layer move to the first interfacial layer and the second interfacial layer, each of the first oxide layer and the second oxide layer has different interfacial properties,
If the first film belongs to any one of the first oxide layer and the second oxide layer, the second film belongs to the other,
In the first cycle process, the gas supply unit supplies each gas in an intermittent mode or a continuous mode,
The continuous mode is a mode in which the first purge gas or the second purge gas is continuously supplied regardless of a supply period of the source gas and the reaction gas,
In the intermittent mode, the first purge gas or the second purge gas is supplied in synchronization with at least one of a supply time point of the source gas, a supply end point of the source gas, a supply time of the reaction gas, and a supply end point of the reaction gas. or the aborted mode,
A second cycle process is performed after the first cycle process,
A time point at which the continuous mode or intermittent mode is selected in the first cycle process and a time point at which the continuous mode or intermittent mode is selected in the second cycle process are different from each other.

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