CN110527981B - Atomic layer deposition equipment and method - Google Patents

Atomic layer deposition equipment and method Download PDF

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CN110527981B
CN110527981B CN201810873257.6A CN201810873257A CN110527981B CN 110527981 B CN110527981 B CN 110527981B CN 201810873257 A CN201810873257 A CN 201810873257A CN 110527981 B CN110527981 B CN 110527981B
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precursor
solvent
valve
reaction chamber
transmission pipeline
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CN110527981A (en
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秦海丰
史小平
兰云峰
纪红
赵雷超
张文强
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Beijing Naura Microelectronics Equipment Co Ltd
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Beijing Naura Microelectronics Equipment Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/4401—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber
    • C23C16/4408—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber by purging residual gases from the reaction chamber or gas lines
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45544—Atomic layer deposition [ALD] characterized by the apparatus
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses atomic layer deposition equipment and an atomic layer deposition method. The equipment comprises a reaction chamber, a solvent flushing system and a plurality of precursor transmission systems, wherein each precursor transmission system comprises a precursor transmission pipeline and a precursor source bottle which is connected with the precursor transmission pipeline in a switchable manner, and the precursor transmission pipelines are commonly converged into the reaction chamber; the solvent flushing system comprises a solvent transmission pipeline and a solvent source bottle which is connected with the solvent transmission pipeline in a switchable manner, and the solvent transmission pipeline is selectively communicated with at least one precursor transmission pipeline so as to introduce a purging solvent into the precursor transmission pipeline and/or the reaction chamber for purging. The invention can reduce the deposition of unexpected reactants in the cavity, improve the purity of the film and improve the quality of the deposited film; the uniformity of the film thickness can be improved, and the repeatability of the film performance among the sheets can be improved; and the adhesion of particles on the inner wall of the chamber can be reduced, thereby improving the purity of the deposited film.

Description

Atomic layer deposition equipment and method
Technical Field
The present invention relates to the field of semiconductor integrated circuit fabrication, and in particular, to an atomic layer deposition apparatus and method.
Background
Zirconia (ZrO 2) is a good oxygen ion conductor that can be used for solid electrodes such as on fuel cells. And ZrO2 can be used for a high-k (high dielectric constant) dielectric layer on the integrated circuit due to the high dielectric constant.
ZrO2 deposited by atomic layer deposition (Atomic layer deposition, ALD) has been used in the form of ZAZ (ZrO 2-Al2O3-ZrO 2) multilayer structures on the capacitance of dynamic random access memories (Dynamic Random Access Memory, DRAM). In thin film deposition, especially ALD deposition, the crystal size of ZrO2 can be controlled by blocking grain growth by laminating ZrO2 with other amorphous layers such as alumina (Al 2O 3).
For ALD reactions of low vapor pressure precursors, improving film uniformity and film performance repeatability between wafers is a major challenge for process optimization because, for ZrO2 deposition, both zirconium halides and zirconium alkoxides and other organometallic precursors are used, which are commonly characterized by low vapor pressure at ambient temperature, difficult control of source bottle heating temperature and vapor pressure, and easy particle generation.
In the prior art, the process steps of ALD deposition of ZrO2 using TEMAZ as a precursor are shown in FIG. 1. A first step of carrying precursor TEMAZ vapor with a carrier gas such as inert gas N2 into the chamber and adsorbing on the substrate; purging the precursor TEMAZ pipeline and the chamber by adopting inert gas, namely, enabling the inert gas to reach the chamber; thirdly, carrying steam of oxide H2O by carrier gas to the chamber and reacting with precursor TEMAZ saturated adsorbed on the substrate; and fourthly, purging the oxide H2O pipeline by adopting inert gas. The above four steps are repeated until the desired thickness is reached.
The existing ALD reaction system has the following disadvantages:
1. the blind short of the gas path and the block, the measurement branch and the like are all positions where the flow speed of the source steam is low or even stagnates, the source steam residue can be condensed to form particles, the ordinary purging is difficult to thoroughly remove, and the accumulated source steam is easy to corrode and agglomerate;
2. in the process of forming ZrO2 by ALD reaction, the purging time of the precursor TEMAZ after entering the chamber is short, and more serious, the viscosity of the TEMAZ is high, so that the residual precursor is difficult to completely remove by common purging. Precursor residues remained in the spaces such as a transmission pipeline, a gas distribution device, the inner wall of the chamber and the like are adsorbed, unexpected ALD reaction occurs, and particles are generated to pollute the chamber and the thin film;
3. during the process, some of the concentrated TEMAZ precursor may desorb and migrate to the local surface of the substrate, and parasitic growth with H2O occurs, thus producing thicker films in these areas, poorer film quality, and affecting overall film thickness uniformity;
4. the parasitic growth inside the chamber, which is difficult to control, not only affects the thickness uniformity, but also worsens the chamber process environment, and the direct effect is that the performance such as the thickness uniformity of the thin film formed by the ALD process is poor and the repeatability between sheets is reduced as time goes on.
FIG. 2a is a graph showing the thickness distribution of a ZrO2 film formed at the initial stage of chamber deposition, and FIG. 2b is a graph showing the thickness distribution of a ZrO2 film formed after a lapse of a period of time during which ZrO2 of about 50nm was deposited in the chamber. Table 1 is a detail of the thickness of both films. Overall, the uniformity of film thickness in the initial stage of chamber deposition is good, and the difference between the maximum value and the minimum value of the thickness on the same piece is small. However, as the deposition time increases, the uniformity of film thickness decreases and the on-chip thickness gap increases significantly after a period of deposition. The edge area is thinner in thickness distribution pattern. The reason for the thinner edge thickness is more numerous, for example, concentration of precursor TEMAZ at the inner wall of the chamber, lack of precursor at the edge during deposition, adsorption unsaturation, etc. The thickness profile also presents the structural shape of the gas distribution device, which is related to the adsorption of the precursor by the gas distribution device structure.
TABLE 1
Figure BDA0001752658330000031
The information disclosed in the background section of the invention is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides an atomic layer deposition device and an atomic layer deposition method, which furthest reduce the residues of low-vapor-pressure precursors in a pipeline and a cavity through improving the atomic layer deposition device and the atomic layer deposition process, thereby reducing the possibility of adsorption and desorption and other unexpected reactions on the inner wall of the cavity of a transmission pipeline; by increasing the formation of the passivation layer, the deposition environment of the chamber in the later deposition period is improved, so that the thickness uniformity and the process repeatability of the deposited film are improved.
According to an aspect of the present invention, an atomic layer deposition apparatus is presented. The apparatus includes a reaction chamber, a solvent flush system, and a plurality of precursor delivery systems, wherein,
each precursor transmission system comprises a precursor transmission pipeline and a precursor source bottle which is connected with the precursor transmission pipeline in an on-off mode, and a plurality of precursor transmission pipelines are commonly gathered into the reaction chamber;
the solvent flushing system comprises a solvent transmission pipeline and a solvent source bottle which is connected with the solvent transmission pipeline in a switchable manner, and the solvent transmission pipeline is selectively communicated with at least one precursor transmission pipeline so as to introduce a purging solvent into the precursor transmission pipeline and/or the reaction chamber for purging.
Preferably, the solvent flushing system further comprises a solvent recovery device and a solvent purification device connected, wherein,
the solvent recovery device comprises a first solvent recovery device and a second solvent recovery device, a plurality of precursor transmission pipelines are connected with the first solvent recovery device in an on-off mode through an afflux pipeline, and the reaction chamber is connected with the second solvent recovery device in an on-off mode.
Preferably, the apparatus further comprises a vacuum pump connected to one of the outlet ends of the reaction chamber via a butterfly valve, the valve core of the butterfly valve being in a constant angle mode.
Preferably, in each of the precursor delivery systems, the precursor source vial is in an on-off connection with the precursor delivery line via a first valve assembly, wherein,
the first valve assembly comprises three pneumatic valves and three manual valves, and the first pneumatic valve is arranged on the precursor transmission pipeline;
the second pneumatic valve and the second manual valve are connected in series and then arranged between the inlet end of the first pneumatic valve and the inlet end of the precursor source bottle;
the third pneumatic valve and the third manual valve are connected in series and then arranged between the outlet end of the first pneumatic valve and the outlet end of the precursor source bottle;
one end of the first manual valve is connected between the second pneumatic valve and the second manual valve, and the other end of the first manual valve is connected between the third pneumatic valve and the third manual valve.
Preferably, the solvent source bottle is connected to the solvent delivery line in an on-off manner by a second valve assembly, wherein,
the second valve assembly comprises three pneumatic valves and two manual valves, the fourth pneumatic valve and the fourth manual valve are connected in series and then connected to the inlet end of the solvent source bottle, and the fifth pneumatic valve and the fifth manual valve are connected in series and then connected to the outlet end of the solvent source bottle;
one end of the sixth pneumatic valve is connected between the fourth pneumatic valve and the fourth manual valve, and the other end of the sixth pneumatic valve is connected between the fifth pneumatic valve and the fifth manual valve.
Preferably, the atomic layer deposition device further comprises an additional gas transmission pipeline, the other outlet end of the reaction chamber is provided with a control valve, the outlet of the control valve is connected with the additional transmission pipeline, and a mass flow controller is arranged at the inlet of the additional transmission pipeline.
Preferably, the solvent delivery pipeline and the precursor delivery pipeline are both provided with heating devices.
According to another aspect of the present invention, an atomic layer deposition method is presented. The method comprises the following steps:
step 1, carrying a first precursor by inert gas into a reaction chamber of atomic layer deposition equipment and then adsorbing the first precursor on the surface of a substrate;
step 2, purging a first precursor transmission pipeline by inert gas;
step 3, inert gas carries a second precursor to enter the reaction chamber and then reacts with the first precursor on the surface of the substrate so as to form a preset film on the substrate;
step 4, purging the second precursor transmission pipeline by inert gas;
step 5, judging whether the film performance of the preset film on any one substrate and the adjacent substrate is poor, if not, repeating the steps 1 to 4 for a plurality of times; if yes, the following step 6 is executed;
and 6, purging the first precursor transmission pipeline and/or the second precursor transmission pipeline and/or the reaction chamber by inert gas carrying solvent vapor.
Preferably, the method further comprises the steps of;
step 7, carrying a third precursor into the reaction chamber by inert gas, and then adsorbing the third precursor on the inner wall of the reaction chamber and the surface of the baffle plate on the substrate;
step 8, purging a third precursor transmission pipeline by inert gas;
step 9, inert gas carries a fourth precursor to enter the reaction chamber and then reacts with the third precursor to form a passivation layer;
step 10, purging the fourth precursor transmission pipeline by inert gas.
Preferably, the first precursor and the third precursor are different kinds of precursors, and the second precursor and the fourth precursor are the same kind of precursor.
Preferably, the preset film is a ZrO2 film, and the passivation layer is an Al2O3 passivation layer.
The invention has the following beneficial technical effects:
aiming at the characteristics of low vapor pressure and viscous property of the precursor, the precursor pipeline and the cavity are purged by the flushing solvent, so that the residue of the precursor in the transmission pipeline is effectively removed, the adsorption of the precursor on the inner wall of the cavity, particularly on the local position with low temperature, is reduced, the deposition of unexpected reactants in the cavity can be reduced, the purity of the film is improved, and the quality of the deposited film is improved;
forming a chamber passivation layer through ALD reaction, covering a small amount of precursor adsorption which cannot be removed through solvent purging in the chamber, and maximally recovering the chamber to an ideal process state so as to improve the uniformity of the thickness of the film and the repeatability of the film performance among the sheets; and the adhesion of particles on the inner wall of the chamber can be reduced, thereby improving the purity of the deposited film.
The method of the present invention has other features and advantages which will be apparent from or are set forth in detail in the accompanying drawings and the following detailed description, which are incorporated herein, and which together serve to explain certain principles of the invention.
Drawings
The foregoing and other objects, features and advantages of the invention will be apparent from the following more particular descriptions of exemplary embodiments of the invention as illustrated in the accompanying drawings wherein like reference numbers generally represent like parts throughout the exemplary embodiments of the invention.
FIG. 1 shows a flow chart of an atomic layer deposition process in the prior art;
FIGS. 2a and 2b are graphs of film thickness profiles during initial deposition and after a period of deposition;
fig. 3 shows a structural diagram of an atomic layer deposition apparatus according to an exemplary embodiment of the present invention;
fig. 4 shows a flowchart of an atomic layer deposition method according to an exemplary embodiment of the present invention.
The main reference numerals illustrate:
a reaction chamber, 2 gas mixing device, 3 substrate, 4 susceptor, 5 vacuum pump, 6 butterfly valve, 7 carrier gas, 10 chamber injection port, 20 chamber output port, 11, 12 precursor source bottle, 13 solvent source bottle, 14 solvent recovery device, 15, 16, 17, 18 mass flow controller, 21, 22 precursor transfer line, 23 solvent transfer line, 24 inert gas transfer line, 25 first precursor transfer line, 26 second precursor transfer line, 27 first inert gas transfer line, 28 second inert gas transfer line, 29 additional gas transfer line, 101-109 control valve, 111, 114 first pneumatic valve, 112, 115 second pneumatic valve, 113, 116 third pneumatic valve, 117 fourth pneumatic valve, 118 fifth pneumatic valve, 119 sixth pneumatic valve, 121, 124 first manual valve, 122, 125 second manual valve, 123, 126 third manual valve, 127 fourth manual valve, 128, fifth manual valve, 141 first solvent device, 142 second solvent recovery device.
Detailed Description
The invention will be described in more detail below with reference to the accompanying drawings. While the preferred embodiments of the present invention are illustrated in the drawings, it should be understood that the present invention may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
Fig. 3 shows a structural diagram of an atomic layer deposition apparatus according to an exemplary embodiment of the present invention. The device mainly comprises: a reaction chamber, a solvent flushing system, and a plurality of precursor delivery systems. For simplicity, fig. 3 shows only two of the precursor delivery systems, the other precursor delivery systems not being shown in the figure, and the structure being similar to that shown.
As shown in fig. 3, the reaction chamber 1 includes a gas mixing device (showhead) 2 provided at the top and a susceptor 4 provided at the bottom, a substrate (wafer) 3 disposed on the susceptor 4, and a thin film formed by a precursor reaction is deposited on the substrate 3. The purpose of the gas mixing device 2 is to enable a uniform distribution of the precursor over the substrate 3, if a gas mixture is used even if it is uniformly mixed. Reference numeral 7 denotes a carrier gas, which is typically an inert gas such as argon, helium, nitrogen, etc., that carries the precursor into the reaction chamber and performs piping and chamber purging.
In the atomic layer deposition equipment, each precursor transmission system comprises a precursor transmission pipeline and a precursor source bottle which is connected with the precursor transmission pipeline in a switchable manner, and a plurality of precursor transmission pipelines are commonly led into the reaction chamber;
the solvent flushing system comprises a solvent transmission pipeline and a solvent source bottle which is connected with the solvent transmission pipeline in a switchable manner, and the solvent transmission pipeline is selectively communicated with at least one precursor transmission pipeline so as to introduce a purging solvent into the precursor transmission pipeline and/or the reaction chamber for purging.
As shown in fig. 3, the gas delivery system includes a precursor delivery line 21, a precursor delivery line 22, and a precursor source bottle 11, a precursor source bottle 12, and a gas delivery line 21 and a gas delivery line 22, which are connected to the precursor delivery line 21 and the precursor delivery line 22 in a switchable manner, respectively, and together join into the reaction chamber 1, and the junction point thereof is referred to as the chamber injection end 10. Inert gas may enter the reaction chamber 1 through the precursor delivery line 21 and/or the precursor delivery line 22.
When the precursor source bottle is heated to a certain degree, precursor steam is generated, and at the moment, when the precursor source bottle is filled with inert gas, the precursor steam is taken out of the precursor source bottle by the inert gas.
When the precursor transmission pipeline 21 is communicated with the precursor source bottle 15, the inert gas introduced into the precursor transmission pipeline 21 carries the precursor in the precursor source bottle 15 out and transmits the precursor in the pipeline; when the precursor transfer line 21 is disconnected from the precursor source bottle 11, the inert gas introduced into the precursor transfer line 21 does not carry the precursor and is directly transferred in the line. The same is true for the precursor delivery line 22 and the precursor source vial 12.
The solvent flushing system comprises a solvent transmission pipeline 23 and a solvent source bottle 13 which is connected with the solvent transmission pipeline 23 in a switchable manner, wherein the solvent transmission pipeline 13 is selectively communicated with the precursor transmission pipeline 21 so as to introduce a purging solvent into the precursor transmission pipeline 21 and/or the reaction chamber 1 for purging.
The solvent flushing system further comprises a solvent recovery device 14 and a solvent purification device (not shown in fig. 3) connected, wherein the solvent recovery device comprises a first solvent recovery device 141 and a second solvent recovery device 142, and the precursor transfer line 21 and the precursor transfer line 22 are connected to the first solvent recovery device 141 in an on-off manner by a converging line, and the reaction chamber 1 is connected to the second solvent recovery device 142 in an on-off manner.
By introducing a flushing solvent into the precursor delivery line connected to the reaction chamber 1, the precursor delivery line or along with the reaction chamber 1 may be solvent flushed, thereby reducing the likelihood of adsorption and desorption and unintended reactions occurring in the precursor delivery line and the inner walls of the reaction chamber 1.
By recovering the flush solvent, the recovered solvent can be re-purified using a solvent purification device. The solvent purification may be carried out by physical separation such as distillation or chemical purification such as catalytic purification. The flushing solvent may be selected based on the precursor nature of the ALD reaction and the reaction temperature characteristics.
The flushing solvent is in a liquid state in the solvent source bottle 13, and when the solvent source bottle 13 is communicated with the solvent transmission pipeline 23, inert gas entering the solvent transmission pipeline 23 enters the solvent source bottle 13, carries out solvent vapor, continues to be transmitted in the pipeline, and reaches the precursor transmission pipeline 21. The first solvent recovery device 141 is connected to the precursor delivery line 21 to recover the flushing solvent after flushing the line. The junction of solvent delivery line 23 and precursor delivery line 21 is referred to as solvent delivery junction 30.
The atomic layer deposition apparatus further comprises a vacuum pump 5, and a transmission pipeline 21 is selectively communicated with the reaction chamber 1 or the vacuum pump 1.
In particular, the selective communication of the precursor delivery line 21 with the reaction chamber 1 and the vacuum pump may be achieved in the following way.
The precursor delivery line 21 is divided into two branches, a first precursor delivery branch 25 and a second precursor delivery branch 26, the first precursor delivery branch 25 being connected to the chamber injection end 10, the second precursor delivery branch 26 being connected to the inlet end of the vacuum pump 5, the connection point being referred to as the chamber output end 20. A control valve 107 is preferably provided between the chamber injection port 10 and the reaction chamber 1, and a control valve 108 is preferably provided between the chamber output port 20 and the vacuum pump 5. The chamber injection port 10 and the chamber output port 20 are connected to the first solvent recovery device 141 and the second solvent recovery device 142, respectively, and the control valve 105 and the control valve 106 are preferably provided on the connection lines.
A control valve 101 and a control valve 102 are provided on the first precursor delivery branch 25 and the second precursor delivery branch 26, respectively. When the control valve 101 is open, the control valve 102 is closed and the gas in the precursor delivery line 21 enters the first precursor branch 25. At this time, when the control valve 107 is opened and the control valve 105 is closed, the gas may then enter the reaction chamber 1, and vice versa, the first solvent recovery device 141. When the control valve 101 is closed, the control valve 102 is opened and the gas in the precursor delivery line 21 enters the second precursor branch 26. At this time, when the control valve 108 is opened and the control valve 106 is closed, the gas is sucked by the vacuum pump 5, and conversely, enters the second solvent recovery device 142.
Based on the above structure, when the solvent system is used for introducing the flushing solvent into the precursor conveying pipeline, only the precursor conveying pipeline which is conveyed by the precursor can be selectively flushed, and the precursor conveying pipeline and the reaction chamber can be optionally flushed together. After both flushing methods, the solvent will enter the solvent recovery device 14 for recovery.
In one example, the vacuum pump 5 is connected to one of the outlet ends of the reaction chamber 1 via a butterfly valve 6, and the valve core of the butterfly valve is in a constant angle mode.
The atomic layer deposition apparatus further comprises an inert gas delivery line 24 and is provided with a mass flow controller 17 at its inlet to control the flow of gas delivered in the line.
The inert gas transfer line 24, like the precursor transfer line 21, is selectively in communication with the reaction chamber 1 or with the 1 vacuum pump, by: the inert gas delivery line 24 is split into a first inert gas delivery branch 27 and a second inert gas delivery branch 28 at the outlet end of the mass flow controller 17, the first inert gas delivery branch 27 merging with the first precursor delivery branch 25 and then being connected to the chamber injection end 10, and the second inert gas delivery branch 28 merging with the second precursor delivery branch 26 and then being connected to the chamber output end 20. The first inert gas transfer branch 27 and the second inert gas transfer branch 28 are preferably provided with a control valve 103 and a control valve 104, respectively.
The ALD reaction has certain requirements on the chamber pressure, and the chamber pressure can be maintained in a proper range by controlling the flow of inert gas in the inert gas transmission pipeline 24 of the gas transmission pipeline through the mass flow controller 17 and controlling the opening angle of the butterfly valve 6 at the bottom of the chamber; and the pressure of the chamber can be changed by adjusting the opening angle of the butterfly valve.
Mass flow controllers 15 and 16 are provided at the inlet ends of the precursor delivery line 21 and the precursor delivery line 22, respectively, to control the flow of gas delivered in the lines.
In one example, both precursor source cylinders 11 and 12 are connected to the precursor delivery lines 21 and 22, respectively, by a first valve assembly.
The first valve assembly is preferably implemented using three pneumatic valves and three manual valves. Taking the first valve assembly for controlling the on/off of the precursor transfer line 21 and the precursor source vessel 11 as an example, it includes a first pneumatic valve 111, a second pneumatic valve 112, a third pneumatic valve 113, a first manual valve 121, a second manual valve 122, and a third manual valve 123. The first pneumatic valve 111 is disposed on the precursor transmission pipeline 21, the second pneumatic valve 112 and the second manual valve 122 are serially connected and then disposed between an inlet end of the first pneumatic valve 111 and an inlet end of the precursor source bottle 11, the third pneumatic valve 113 and the third manual valve 123 are serially connected and then disposed between an outlet end of the first pneumatic valve 111 and an outlet end of the precursor source bottle 11, one end of the first manual valve 121 is connected between the second pneumatic valve 112 and the second manual valve 122, and the other end is connected between the third pneumatic valve 113 and the third manual valve 123.
When the first pneumatic valve 111 is opened, the second pneumatic valve 112 and the third pneumatic valve 113 are closed, the inert gas in the precursor transmission pipeline 21 bypasses the precursor source bottle 11, and is directly transmitted in the pipeline without carrying the precursor; with the first pneumatic valve 111 closed and the second pneumatic valve 112, the third pneumatic valve 113 and the second and third manual valves 122, 123 open, inert gas passes through the precursor source cylinder 11 and carries the precursor out of the precursor source cylinder 11 for delivery in a pipeline.
Other precursor delivery lines and corresponding precursor source vials may be similarly configured.
The solvent delivery connection point 30 is preferably located at the outlet end of the third pneumatic valve 113. Since the outlet end of the precursor source 11 is a portion where more precursor is accumulated, connecting the solvent delivery line 23 to the outlet end of the third pneumatic valve 113 is more advantageous for thoroughly flushing the precursor remaining in the line.
In one example, the solvent source bottle 13 is connected to the solvent delivery line 23 by a second valve assembly.
The second valve assembly is preferably implemented using a combination of three pneumatic valves and two manual valves, including, for example, a fourth pneumatic valve 117, a fifth pneumatic valve 118, a sixth manual valve 119, a fourth manual valve 127, and a fifth manual valve 128. Wherein the fourth pneumatic valve 117 and the fourth manual valve 127 are connected in series and then connected to the inlet end of the solvent source bottle 13; the fifth pneumatic valve 118 and the fifth manual valve 128 are connected in series and then connected to the outlet end of the solvent source bottle 13; the sixth pneumatic valve 119 has one end connected between the fourth pneumatic valve 117 and the fourth manual valve 127 and the other end connected between the fifth pneumatic valve 118 and the fifth manual valve 128.
With the fourth 117, fifth 118, sixth 119 pneumatic valves open and the fourth 127, fifth 128 manual valves closed, the inert gas in the solvent transfer line 23 bypasses the solvent source bottle 13, transferring directly in the line without carrying solvent; with the sixth pneumatic valve 119 closed and the fourth pneumatic valve 117, fifth pneumatic valve 118 and fourth manual valve 127, fifth manual valve 128 open, inert gas passes through the solvent source bottle 13 and carries solvent out of the solvent source bottle 13 for transfer in a pipeline.
At one of the outlet ends of the reaction chamber 1 a control valve 108 is provided, an additional gas transfer line 29 is connected to the outlet end of the control valve 108, and a mass flow controller 18 is provided on the additional gas transfer line 29.
The purpose of the additional gas transfer line 29 is to reduce particles generated by the opening and closing of the chamber valve. The particle pollution caused by the opening and closing actions of the gate valve can be reduced by increasing the purging of inert gas to the gate valve position.
In one example, heating means are provided on both the rinse solution delivery line 23 and the precursor delivery line 21.
The flushing solvent carried from the flushing solvent source bottle 13 is typically solvent vapor, and in order to prevent re-condensation of the solvent vapor, heating control means, such as heating tape, is added to both the solvent delivery line 23 and the precursor delivery line 21 to perform proper heating control.
Fig. 4 shows a flowchart of an atomic layer deposition method according to an exemplary embodiment of the present invention. As shown in fig. 4, the method includes S101 to S107.
In step S101, an inert gas carries a first precursor into a reaction chamber of an atomic layer deposition apparatus and then is adsorbed on a surface of a substrate.
Inert gas is used as carrier gas for the precursor, which may be argon, helium, nitrogen, etc.
In step S102, the inert gas purges the first precursor delivery line.
And removing residual precursor in the precursor transmission pipeline and the reaction chamber by purging with inert gas and matching with vacuumizing.
In step S103, the inert gas carries the second precursor into the reaction chamber and then reacts with the first precursor on the surface of the substrate to form a predetermined thin film.
The types of the first precursor and the second precursor are determined based on the type of the predetermined thin film, for example, zrO 2 A film.
In step S104, the inert gas purges the second precursor delivery line.
Similar to step S102, residual precursor in the precursor transfer line and the reaction chamber is removed by purging with an inert gas in combination with evacuation.
In step S105, it is determined whether the film properties of the preset film on any one substrate and the adjacent substrate are degraded, if not, steps S101 to S104 are repeatedly performed for a plurality of times; if so, step S106 is performed.
It is mainly determined whether the uniformity of the thin film is rather deteriorated with an increase in the accumulated thickness of the thin film.
In step S106, the inert gas carries the solvent vapor to purge the first precursor delivery line and/or the second precursor delivery line and/or the reaction chamber.
The inert gas carrying the solvent vapor sweeps the first precursor transmission pipeline and/or the second precursor transmission pipeline and/or the reaction chamber so as to effectively remove the residues of the precursor in the precursor transmission pipeline, reduce the adsorption of the precursor on the inner wall of the chamber, especially on the local position with low temperature, and reduce the deposition of unexpected reactants in the chamber, thereby improving the purity of the film and the quality of the deposited film.
In one example, the method further comprises steps S107-S110.
In step S107, the inert gas carries the third precursor into the reaction chamber and then is adsorbed on the inner wall of the reaction chamber and the surface of the baffle plate on the substrate.
In step S108, the inert gas purges the third precursor delivery line.
In step S109, the inert gas carries the fourth precursor into the reaction chamber and reacts with the third precursor to form a passivation layer, such as Al 2 O 3 And a passivation layer.
In step S110, the inert gas purges the fourth precursor delivery line.
The cavity passivation layer is formed through ALD reaction, so that not only can a small amount of precursor adsorption which cannot be removed through solvent purging be covered in the cavity, but also the cavity can be restored to an ideal process state to the greatest extent, and therefore the uniformity of the thickness of the film is improved, and particularly the repeatability of the film performance among sheets is improved. The adhesion of particles on the inner wall of the chamber can be reduced by the passivation layer, so that the purity of the deposited film is improved.
The first precursor and the third precursor are different kinds of precursors, and the second precursor and the fourth precursor are the same kind of precursor.
Before step S107, the lines for transporting the first precursor and the second precursor are preferably purged with an inert gas, and the solvent is purged by vacuum to purge the gas lines of the post-purge gas lines of the precursor transfer lines and the particle residues in the chamber.
Prior to step S101, all gas delivery line precursor delivery lines are preferably purged with an inert gas to provide a good substrate surface for the ALD reaction.
Based on the types of the precursors utilized by the atomic layer deposition method, the number of precursor conveying pipelines and corresponding precursor source bottles contained in the gas conveying system of the atomic layer deposition equipment is determined, namely the atomic layer deposition equipment can be utilized to implement the method.
Application example
The process of depositing a film by the atomic layer deposition apparatus shown in fig. 3 will be described below by taking a deposited zirconia film as an example.
(1) The inert gas nitrogen is adsorbed on the surface of the substrate 3 after entering the reaction chamber 1 with the precursor TEMAZ vapor from the precursor transfer line 21.
In the precursor delivery line 21, a certain amount of inert gas controlled by the mass flow controller 15 is introduced into the source bottle 11 (for example, heated to 80 ℃) of the precursor TEMAZ with temperature controlled by heating through the second pneumatic valve 112 and the second manual valve 122, and TEMAZ vapor is carried by the carrier gas, returned to the precursor delivery line 21 through the third manual valve 123 and the third pneumatic valve 113, and then enters the reaction chamber 1 through the control valves 101 and 107. The precursor TEMAZ pulses are uniformly adsorbed on the surface of the substrate 3 after passing through the gas distribution means 2 at the upper part of the chamber.
(2) The inert gas purges the precursor delivery line 21.
With the first pneumatic valve 111 open, the second pneumatic valve 112, and the third pneumatic valve 113 closed, inert gas is not transferred through the precursor source bottle 11, i.e., not carrying the precursor in the piping.
The inert gas used for purging may be purged to the precursor delivery line 21 and the reaction chamber by opening the control valves 101, 107, or the purge gas may be purged to only the precursor delivery line 21 without entering the reaction chamber 1 by opening the control valves 102, 108. At the same time, the residual TEMAZ gas in the pipeline and the chamber can be removed by matching with the suction effect of the vacuum pump 5.
(3) Inert gas carries precursor H 2 O enters the reaction chamber 1.
H 2 The O pulse enters the reaction chamber 1 through a precursor delivery line not shown in FIG. 3 to react with the precursor TEMAZ adsorbed on the surface of the substrate to form ZrO on the substrate 2 A film.
(4) Inert gas purge delivery of precursor H 2 O pipeline.
(5)Judging ZrO 2 If the film performance of the front and back films of the film is poor, repeating the steps (1) to (4) for a plurality of times; if yes, executing (6);
(6) Inert gas carrying flushing solvent sweeps TEMAZ transfer line and/or H 2 O transfer lines and/or reaction chambers 1.
The precursor TEMAZ has low vapor pressure and thick property, so that ZrO with certain thickness is deposited 2 And then through the solvent purge chamber and piping. Suitable organic solvents may be used for the flush solvent because these solvents have a suitable vapor pressure.
The inert gas is introduced into the solvent source bottle 13 with the temperature controlled by heating after passing through the fourth pneumatic valve 117 and the fourth manual valve 127, and then carries the flushing solvent vapor out to pass through the fifth manual valve 128 and the fifth pneumatic valve 118 at the outlet of the solvent source bottle 13, passes through the solvent transmission pipeline 23, and enters the solvent transmission pipeline 21 at the solvent transmission connection point 30.
The solvent recovery device 14 can be entered after purging the precursor delivery line 21 and the first precursor delivery line 25 with the flushing solvent vapor by opening the control valves 101, 107; the solvent recovery device 14 may also be purged by the flush solvent vapor through the precursor delivery line 21 and the second precursor delivery line 26 by opening the control valves 102, 108.
(7) Inert gas carrying TMA enters the reaction chamber 1 and is adsorbed on the inner wall of the reaction chamber and the surface of the baffle plate on the substrate.
(8) The inert gas purges the TMA transfer line.
(9) Carry H 2 The inert gas of O enters the reaction chamber 1 and reacts with TMA to form Al 2 O 3 And a passivation layer.
(10) Inert gas purging H 2 And O transmission pipelines.
Formation of Al 2 O 3 H of (2) 2 O and ZrO 2 H of reaction 2 O may share a source bottle.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described. The terminology used herein was chosen in order to best explain the principles of the embodiments, the practical application, or the improvement of technology in the marketplace, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.

Claims (11)

1. An atomic layer deposition device is characterized by comprising a reaction chamber, a solvent flushing system, a vacuum pump and a plurality of precursor delivery systems, wherein,
each precursor transmission system comprises a precursor transmission pipeline and a precursor source bottle which is connected with the precursor transmission pipeline in an on-off mode, and a plurality of precursor transmission pipelines are commonly gathered into the reaction chamber;
the solvent flushing system comprises a solvent transmission pipeline and a solvent source bottle which is connected with the solvent transmission pipeline in a switchable manner, and the solvent transmission pipeline is selectively communicated with at least one precursor transmission pipeline so as to introduce a purging solvent into the precursor transmission pipeline and the reaction chamber for purging;
the connection point of the solvent transmission pipeline and the precursor transmission pipeline is a solvent transmission connection point, and the solvent transmission connection point is positioned at the outlet end of the precursor source bottle;
the precursor transmission pipeline comprises a first precursor transmission branch and a second precursor transmission branch which are positioned at the downstream of the solvent transmission connection point and connected in parallel, and the first precursor transmission branch is connected to the inlet end of the reaction chamber; the second precursor transmission branch is connected to the inlet end of the vacuum pump, and the outlet end of the reaction chamber is communicated with the inlet end of the vacuum pump; the first precursor transmission branch and the second precursor transmission branch are respectively provided with a first control valve and a second control valve.
2. The atomic layer deposition apparatus according to claim 1, wherein the solvent flushing system further comprises a solvent recovery device and a solvent purification device connected, wherein,
the solvent recovery device comprises a first solvent recovery device and a second solvent recovery device, a plurality of precursor transmission pipelines are connected with the first solvent recovery device in an on-off mode through an afflux pipeline, and the reaction chamber is connected with the second solvent recovery device in an on-off mode.
3. The atomic layer deposition apparatus according to claim 2, wherein the vacuum pump is connected to one of the outlet ends of the reaction chamber via a butterfly valve, the valve core of which is in a constant angle mode.
4. The atomic layer deposition apparatus according to claim 2, wherein in each of the precursor delivery systems, the precursor source vessel is connected to the precursor delivery line by a first valve assembly, wherein,
the first valve assembly comprises three pneumatic valves and three manual valves, and the first pneumatic valve is arranged on the precursor transmission pipeline;
the second pneumatic valve and the second manual valve are connected in series and then arranged between the inlet end of the first pneumatic valve and the inlet end of the precursor source bottle;
the third pneumatic valve and the third manual valve are connected in series and then arranged between the outlet end of the first pneumatic valve and the outlet end of the precursor source bottle;
one end of the first manual valve is connected between the second pneumatic valve and the second manual valve, and the other end of the first manual valve is connected between the third pneumatic valve and the third manual valve.
5. The atomic layer deposition apparatus according to claim 4, wherein the solvent source bottle is connected to the solvent transfer line by a second valve assembly, wherein,
the second valve assembly comprises three pneumatic valves and two manual valves, the fourth pneumatic valve and the fourth manual valve are connected in series and then connected to the inlet end of the solvent source bottle, and the fifth pneumatic valve and the fifth manual valve are connected in series and then connected to the outlet end of the solvent source bottle;
one end of the sixth pneumatic valve is connected between the fourth pneumatic valve and the fourth manual valve, and the other end of the sixth pneumatic valve is connected between the fifth pneumatic valve and the fifth manual valve.
6. The atomic layer deposition apparatus according to claim 4, further comprising an additional gas delivery line, wherein a control valve is provided at the other outlet end of the reaction chamber, wherein an outlet of the control valve is connected to the additional delivery line, and wherein a mass flow controller is provided at an inlet of the additional delivery line.
7. The atomic layer deposition apparatus according to claim 2, wherein a heating device is provided on both the solvent delivery line and the precursor delivery line.
8. An atomic layer deposition method, comprising the steps of:
step 1, carrying a first precursor by inert gas into a reaction chamber of atomic layer deposition equipment and then adsorbing the first precursor on the surface of a substrate;
step 2, purging a first precursor conveying pipeline by inert gas;
step 3, inert gas carries a second precursor to enter the reaction chamber and then reacts with the first precursor on the surface of the substrate so as to form a preset film on the substrate;
step 4, purging the second precursor transmission pipeline by inert gas;
step 5, judging whether the film performance of the preset film on any one substrate and the adjacent substrate is poor, if not, repeating the steps 1 to 4 for a plurality of times; if yes, the following step 6 is executed;
and 6, purging the first precursor transmission pipeline and/or the second precursor transmission pipeline and the reaction chamber by taking inert gas carrying solvent vapor as a purging starting point from the outlet end of the precursor source bottle.
9. The atomic layer deposition method according to claim 8, further comprising the steps of:
step 7, carrying a third precursor into the reaction chamber by inert gas, and then adsorbing the third precursor on the inner wall of the reaction chamber and the surface of the baffle plate on the substrate;
step 8, purging a third precursor transmission pipeline by inert gas;
step 9, inert gas carries a fourth precursor to enter the reaction chamber and then reacts with the third precursor to form a passivation layer;
step 10, purging the fourth precursor transmission pipeline by inert gas.
10. The atomic layer deposition method according to claim 9, wherein the first precursor and the third precursor are different species precursors, and the second precursor and the fourth precursor are the same species precursor.
11. The atomic layer deposition method according to claim 10, wherein the predetermined thin film is a ZrO2 thin film and the passivation layer is an Al2O3 passivation layer.
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CN107868944B (en) * 2017-10-31 2020-02-07 北京北方华创微电子装备有限公司 Titanium nitride atomic layer deposition device and deposition method thereof
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US20090162551A1 (en) * 2007-12-21 2009-06-25 Thomas Zilbauer Hafnium oxide ald process

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