CN110565072B - Atomic layer deposition method - Google Patents

Atomic layer deposition method Download PDF

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CN110565072B
CN110565072B CN201810569904.4A CN201810569904A CN110565072B CN 110565072 B CN110565072 B CN 110565072B CN 201810569904 A CN201810569904 A CN 201810569904A CN 110565072 B CN110565072 B CN 110565072B
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请求不公布姓名
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Changxin Memory Technologies Inc
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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
    • C23C16/455—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
    • C23C16/458—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 supporting substrates in the reaction chamber
    • C23C16/4582—Rigid and flat substrates, e.g. plates or discs
    • C23C16/4583—Rigid and flat substrates, e.g. plates or discs the substrate being supported substantially horizontally
    • C23C16/4584—Rigid and flat substrates, e.g. plates or discs the substrate being supported substantially horizontally the substrate being rotated
    • 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
    • C23C16/52—Controlling or regulating the coating process
    • 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

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  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

The invention belongs to the field of film preparation of integrated circuits, and particularly relates to an atomic layer deposition method, which comprises the following steps: introducing a first reaction gas, wherein a part of the first reaction gas is attached to the surface of the lower electrode; introducing a first cleaning gas to discharge the first reaction gas remained in the reaction chamber; introducing a second reaction gas, wherein the second reaction gas reacts with the first reaction gas to form a first layer of film; introducing a second cleaning gas to discharge the second reaction gas and the reaction byproducts remained in the reaction chamber; the time for introducing the first cleaning gas is an integral multiple of the time for rotating the bearing table for one circle. The method can effectively ensure the effect of each step of deposition, so that the finally obtained film has uniform thickness.

Description

Atomic layer deposition method
Technical Field
The invention belongs to the field of film preparation of integrated circuits, and particularly relates to an atomic layer deposition method.
Background
The Atomic Layer Deposition (ALD) technology is one of the most advanced film deposition technologies at present, and the single-atom layer-by-layer deposition mode adopted by the ALD technology greatly improves the prepared film in the aspects of uniformity, roughness and the like, and other aspects are superior to other deposition modes except that the growth rate is lower.
In atomic layer deposition, ALD reaction precursors need to be able to rapidly react chemically with the substrate material, or surface groups of the substrate material, and reach saturated adsorption to complete thin film deposition.
However, in the case of the thin film prepared by ALD technology in the prior art, the thickness of the deposited thin film is different (1, 2, 3, 4, 5) as shown in FIGS. 1-2; while byproduct particles 6 are present. In order to improve the quality of the deposited film, chinese patent CN1503326a "method for increasing atomic layer deposition rate", which mainly controls the thickness of precursor reaction film by controlling the exhaust valve. However, in practical application, the precursor cannot be cleaned up, and impurities left in the previous film formation can affect the quality of the next film formation when the film formation is repeated. Therefore, it cannot effectively ensure the film forming effect.
Disclosure of Invention
The invention provides an atomic layer deposition method which can effectively ensure the effect of each step of deposition, so that the finally obtained film has uniform thickness.
In order to achieve the technical purpose, the technical scheme adopted by the invention is that the atomic layer deposition method comprises the following steps:
s1, providing a reaction chamber, wherein a rotatable bearing table is arranged in the reaction chamber; the wafer provided with the lower electrode bracket group is loaded on the bearing table;
s2, introducing a first reaction gas into the reaction chamber, wherein a part of the first reaction gas is attached to the surface of the lower electrode bracket group;
s3, cleaning a first chamber, namely performing first vacuumizing treatment on the reaction chamber, and then introducing first cleaning gas into the reaction chamber, wherein the circulation operation from the first vacuumizing treatment to the introduction of the first cleaning gas is performed for two or more times to discharge the first reaction gas suspended and remained in the reaction chamber;
s4, introducing a second reaction gas into the reaction chamber, wherein the second reaction gas reacts with the first reaction gas attached to the surface of the lower electrode bracket set so as to form a first layer of film on the surface of the lower electrode bracket set;
s5, cleaning a second chamber, namely performing second vacuumizing treatment on the reaction chamber, and then introducing the second cleaning gas into the reaction chamber to discharge second reaction gas suspended and remained in the reaction chamber and free byproducts of the reaction of the first reaction gas and the second reaction gas;
and in the processes of the first vacuumizing treatment and the introduction of the first cleaning gas, the bearing table keeps rotating, the time for introducing the first cleaning gas meets the integral multiple relation of the time for rotating the bearing table for one circle, and the number of circulating operation times from the first vacuumizing treatment to the introduction of the first cleaning gas is larger than that from the second vacuumizing treatment to the introduction of the second cleaning gas.
As an improved technical scheme of the invention, the followingThe first reaction gas comprises an oxygen source precursor, and the second reaction gas comprises C 11 H 22 N 3 Zr, and does not chemically react with the first cleaning gas.
As an improved technical scheme of the invention, the first cleaning gas and the second cleaning gas comprise one of inert gas and nitrogen.
As an improved technical scheme of the invention, the time used for the first vacuumizing treatment also meets the integral multiple relation when the bearing table rotates for one circle.
As an improved technical scheme of the invention, the lower electrode bracket group comprises a lower supporting layer, a middle supporting layer, an upper supporting layer and a lower electrode body; the lower support layer, the middle support layer and the upper support layer support the bottom, the middle and the top of the lower electrode body, respectively.
As an improved technical scheme of the invention, the materials of the lower supporting layer, the middle supporting layer and the upper supporting layer comprise silicon nitride; the material of the lower electrode body comprises titanium nitride.
As an improved technical scheme of the invention, the atomic layer deposition method further comprises the following steps: s6, introducing a third reaction gas into the reaction chamber, wherein the third reaction gas is partially attached to the surface of the first layer of film;
s7, cleaning a third chamber, namely performing third vacuumizing treatment on the reaction chamber, and then introducing third cleaning gas into the reaction chamber, wherein the circulation operation from the third vacuumizing treatment to the introduction of the third cleaning gas is performed for two or more times so as to discharge the third reaction gas floating in the reaction chamber;
s8, introducing the fourth reaction gas into the reaction chamber, wherein the fourth reaction gas reacts with the third reaction gas attached to the surface of the first layer of film to form a second layer of film;
s9, cleaning a fourth chamber, namely performing fourth vacuumizing treatment on the reaction chamber, and then introducing the fourth cleaning gas into the reaction chamber to discharge fourth reaction gas suspended and remained in the reaction chamber and free byproducts of the reaction of the third reaction gas and the fourth reaction gas;
and the third vacuumizing treatment and the third cleaning gas are introduced, wherein the bearing table) keeps rotating, the time for introducing the third cleaning gas meets the integral multiple relation when the bearing table rotates for one circle, and the number of circulating operation times from the third vacuumizing treatment to the third cleaning gas is larger than the number of operation times from the fourth vacuumizing treatment to the fourth cleaning gas.
As an improved technical scheme of the invention, the third cleaning gas and the fourth cleaning gas comprise nitrogen.
As an improved technical scheme of the invention, the atomic layer deposition method further comprises S10, introducing a fifth reaction gas into the reaction chamber, wherein the fifth reaction gas is partially attached to the surface of the second layer of film;
s11, cleaning a fifth chamber, namely performing fifth vacuumizing treatment on the reaction chamber, and then introducing fifth cleaning gas into the reaction chamber, wherein the circulation operation from the fifth vacuumizing treatment to the introduction of the fifth cleaning gas is performed for two or more times so as to discharge the fifth reaction gas floating and remaining in the reaction chamber;
s12, introducing the sixth reaction gas into the reaction chamber, wherein the sixth reaction gas reacts with the fifth reaction gas attached to the surface of the second layer of film to form a third layer of film;
s13, cleaning a sixth chamber, namely performing a sixth vacuumizing treatment on the reaction chamber, and then introducing the sixth cleaning gas into the reaction chamber to discharge the sixth reaction gas suspended and remained in the reaction chamber and free byproducts of the reaction of the fifth reaction gas and the sixth reaction gas.
As an improved technical scheme of the invention, the fifth cleaning gas and the sixth cleaning gas comprise nitrogen.
As an improved technical scheme of the invention, the fifth reaction gas comprises an oxygen source precursor, and the sixth reaction gas comprises C 11 H 22 N 3 Zr, and does not chemically react with the fifth cleaning gas.
As an improved technical scheme of the invention, a double sprayer is adopted to introduce the second reaction gas into the reaction chamber.
Advantageous effects
According to the method, the rotating speed of the bearing table is adjusted to coincide with the time for introducing the first cleaning gas to form an integral circle, and the vacuumizing/blowing cycle times of the first reaction gas and the second reaction gas are adjusted, so that residual byproducts on the surface of the wafer are eliminated, dust pollution is reduced, the thickness of the dielectric layer is improved, the quality of the dielectric layer is improved, leakage current loss is reduced, and the yield of products is improved. Meanwhile, the processing time is shortened, and the productivity is improved.
Drawings
FIG. 1 is a schematic diagram showing the film thickness distribution in the prior art.
FIG. 2 is a diagram showing defects existing after the deposition of the prior art thin film.
Fig. 3 is a flow chart of an atomic layer deposition process according to the present application.
Fig. 4 is a schematic structural view of a reaction chamber in the atomic layer deposition apparatus of the present application.
Fig. 5 is a schematic structural diagram of a lower electrode holder set according to the present application.
Fig. 6 is a schematic view of the section a in fig. 5.
FIG. 7 is a schematic diagram illustrating a process of introducing a first reactive gas into the bottom electrode-holder set.
Fig. 8 is a schematic view of the lower electrode holder set after the first cleaning gas is introduced.
Fig. 9 is a schematic diagram illustrating a process of introducing a second reaction gas into the bottom electrode-holder set.
Fig. 10 is a schematic diagram of the structure of the bottom electrode-holder set after the first deposition of the thin film.
FIG. 11 is a schematic view showing the structure of the lower electrode holder set in section B in FIG. 10 after the first deposition of the thin film.
FIG. 12 is a schematic diagram showing the structure of the deposited upper electrode on the dielectric zirconia;
fig. 13 is a schematic structural diagram of a capacitor.
FIG. 14 is a graph showing the thickness distribution of a thin film deposited in comparative example 1 of the present invention.
FIG. 15 is a graph showing the thickness distribution of the deposited film according to example 1 of the present invention.
FIG. 16 is a visual chart showing the film thickness distribution of comparative example 1 and example 1 according to the present invention.
In the figures, 1, 2, 3, 4, 5 respectively represent different thicknesses of films deposited according to the prior art; 6. byproduct particles; 7. a lower electrode holder set; 8. a first film; 9. an upper electrode; 10. a lower support layer; 11. a carrying platform; 12. a first thickness; 13. a second thickness; 14. an intermediate support layer; 15. an upper support layer; 16. a lower electrode body; 17. a first reactant gas; 18. a second reactant gas; 19. polycrystalline silicon; S1-S13; 100. a wafer; 300. a reaction chamber; 301. an air inlet pipe; 302. air holes; 303. an air inlet; 304. and an air outlet.
Detailed Description
The technical scheme of the present invention will be explained in detail with reference to the accompanying drawings and specific embodiments.
The capacitor dielectric layer adopts a furnace tube atomic layer deposition methodAtomic Layer Deposition), the process is mainly subdivided into six steps:
(1) the precursor A enters a reaction chamber to be adsorbed on the surface of a wafer;
(2) vacuumizing the redundant precursor A;
(3) blowing-off treatment is carried out by adopting inert gas;
(4) the precursor B enters a reaction chamber for reaction;
(5) vacuumizing the residual byproducts;
(6) blowing-off treatment is carried out again by adopting inert gas.
Whereby the substance is deposited layer by layer on the substrate surface in the form of a single atomic film.
Specifically, an embodiment of the present invention provides an atomic layer deposition method, as shown in fig. 3, including the following steps:
providing a reaction chamber 300, as shown in fig. 4, wherein a rotatable carrying table 11 is arranged in the reaction chamber 300; the bearing table 11 is arranged at the bottom of the reaction chamber 300, a motor is arranged below the reaction chamber 300, and the motor is in transmission connection with the bearing table 11 and drives the bearing table 11 to rotate at a constant speed; in order to improve the film deposition efficiency, as shown in fig. 5-6, the lower electrode support set 7 is loaded on the bearing table 11, and the lower electrode support set 7 includes a lower support layer 10, an intermediate support layer 14, an upper support layer 15, and a lower electrode body 16; the lower electrode body 16 is connected to the lower support layer 10, the intermediate support layer 14, and the upper support layer 15 at the same time; the lower support layer 10, the middle support layer 14, and the upper support layer 15 support the bottom, middle, and top of the lower electrode body 16, respectively; the lower support layer 10 comprises silicon nitride; the intermediate support layer 14 comprises silicon nitride; the upper support layer 15 comprises silicon nitride; the lower electrode body 16 comprises titanium nitride.
As shown in fig. 4, the lower end of one side of the reaction chamber 300 is provided with an air inlet 303, and the lower end of the other side is provided with an air outlet 304; the air inlet pipe 301 is vertically arranged in the reaction chamber 300 and is communicated with the air inlet 303, the air inlet pipe 301 is used for introducing the first reaction gas 17 into the reaction chamber 300, and a plurality of air holes 302 are formed in the air inlet pipe 301 along the vertical direction; as shown in fig. 7, the first reaction gas 17 is partially attached to the surface of the lower electrode holder set 7;
as shown in fig. 8, the reaction chamber 300 is subjected to a first vacuum pumping treatment through the gas outlet 304, and then the first cleaning gas is introduced into the reaction chamber 300 for the first time through the gas inlet pipe 301; performing a second vacuumizing treatment on the reaction chamber 300, and then introducing the first cleaning gas into the reaction chamber 300 for a second time; performing third vacuumizing treatment on the reaction chamber 300 through the air outlet 304, and then introducing the first cleaning gas into the reaction chamber 300 through the air inlet pipe 301 for the third time; to discharge the first reaction gas 17 remaining in the reaction chamber 300; namely, the first chamber cleaning is performed, which comprises the steps of firstly performing a first vacuumizing treatment on the reaction chamber 300, then introducing a first cleaning gas into the reaction chamber 300, and discharging the first reaction gas 17 suspended and remained in the reaction chamber 300 by performing a circulation operation from the first vacuumizing treatment to the introduction of the first cleaning gas for two or more times;
as shown in fig. 9, a second reaction gas 18 is introduced, and the second reaction gas 18 is introduced into the reaction chamber 300, wherein the second reaction gas 18 reacts with the first reaction gas 17 attached to the surface of the lower electrode holder set 7 to form a first thin film 8 (as shown in fig. 10 and 11);
performing a fourth vacuum pumping treatment on the reaction chamber 300, and introducing the second cleaning gas into the reaction chamber 300 to discharge the second reaction gas 18 remained in the reaction chamber 300 and free byproducts of the reaction between the first reaction gas 17 and the second reaction gas 18; namely, performing second chamber cleaning, including performing a second vacuum pumping treatment on the reaction chamber 300, and then introducing the second cleaning gas into the reaction chamber 300 to discharge the second reaction gas 18 suspended and remained in the reaction chamber 300 and free byproducts of the reaction between the first reaction gas 17 and the second reaction gas 18;
the first reaction gas 17 comprises an oxygen source precursor, and the second reaction gas 18 comprises C 11 H 22 N 3 Zr, and does not chemically react with the first cleaning gas. Or the first reaction gas 17 includes C 11 H 22 N 3 Zr, the second reactant gas 18 includes an oxygen source precursor and does not chemically react with the first cleaning gas.
The time for introducing the first cleaning gas is an integral multiple of the time for rotating the bearing table 11 for one circle; preferably, the time for introducing the second cleaning gas is an integer multiple of the time for rotating the carrying table 11 for one revolution; more preferably, the time taken for the first vacuuming treatment also satisfies the integer multiple relationship when the carrying table 11 rotates once. In other words, during the first vacuuming process and the process of introducing the first cleaning gas, the carrying table 11 keeps rotating, the time for introducing the first cleaning gas satisfies the integral multiple relationship when the carrying table 11 rotates for one circle, and the number of circulation operations from the first vacuuming process to the first cleaning gas is greater than the number of operations from the second vacuuming process to the second cleaning gas.
Here, the rotation speed of the carrying table 11 (the carrying table 11 drives the wafer 100 to rotate) is adjusted to match the time for introducing the first cleaning gas to form an integer number of circles, and the number of times of vacuumizing/blowing cycles of the first cleaning gas and the second cleaning gas is adjusted, so that residual byproducts on the surface of the lower electrode support set 7 are eliminated, dust pollution is reduced, the quality of a dielectric layer is improved, leakage current loss is reduced, and further the yield of products and productivity are improved.
In addition, the material is supplied by the atomizer for deposition, and the second reaction gas 18 is introduced into the reaction chamber 300 from the single atomizer to the double atomizer because the supply amount of the second reaction gas 18 is smaller, so that the adhesion of the second reaction gas 18 on the lower electrode support group 7 can be effectively improved, and the deposition efficiency of the dielectric layer is further improved.
Example 1
Providing a reaction chamber 300, wherein a rotatable carrying table 11 is arranged in the reaction chamber 300, the carrying table 11 has a rotating speed of 3RPM (revolutions per minute), and the time required for one revolution of the carrying table 11 is 20 seconds; loading a wafer 100 provided with a lower electrode bracket group 7 on a bearing table 11; the first reaction gas 17 is introduced: introducing a first reaction gas 17 into the reaction chamber 300 for 90 seconds, wherein the first reaction gas 17 is partially adhered to the surface of the lower electrode bracket group 7; the first reactive gas 17 in this embodiment comprises ozone;
introducing a first cleaning gas: performing a first vacuumizing treatment on the reaction chamber 300, wherein the vacuumizing time is 20 seconds, and then introducing the first cleaning gas into the reaction chamber 300 for the first time, wherein the duration is 20 seconds; performing a second vacuumizing treatment on the reaction chamber 300, wherein the vacuumizing time is 20 seconds, and then introducing the first cleaning gas into the reaction chamber 300 for the second time for 20 seconds; performing third vacuumizing treatment on the reaction chamber 300, wherein the vacuumizing time is 20 seconds, and then third introducing the first cleaning gas into the reaction chamber 300 for 20 seconds; to discharge the first reaction gas 17 remaining in the reaction chamber 300;
introducing a second reactive gas 18, the second reactive gas 18 comprising C 11 H 22 N 3 Zr and does not chemically react with the first cleaning gas; in this embodiment, a second reactive gas 18 is introduced into the reaction chamber 300 for 60 seconds, and the second reactive gas 18 reacts with the first reactive gas 17 attached to the surface of the lower electrode holder set 7 to form a first thin film 8 (as shown in fig. 10-11); in this embodiment, a high-k dielectric layer, zirconium oxide, is deposited on the surface of titanium nitride (bottom electrode body 16);
introducing a second cleaning gas: and performing a fourth vacuumizing treatment on the reaction chamber 300, wherein the vacuumizing time is 20 seconds, and introducing the second cleaning gas into the reaction chamber 300 for 20 seconds to discharge the second reaction gas 18 remained in the reaction chamber 300 and free byproducts of the reaction between the first reaction gas 17 and the second reaction gas 18.
The thickness of the film attached to the lower electrode holder set 7 prepared in this example was measured, and the film thickness was uniformly distributed as shown in fig. 15.
In the preparation of the capacitor, as shown in fig. 12 and 13, the upper electrode 9 and the polysilicon 19 may be deposited on the dielectric layer zirconia, i.e., the capacitor is prepared.
Comparative example 1
Providing a reaction chamber 300, wherein a rotatable carrying table 11 is arranged in the reaction chamber 300, and the carrying table 11 has a rotating speed of 2 RPM; loading a wafer 100 provided with a lower electrode bracket group 7 on a bearing table 11;
introducing a first reaction gas 17, and introducing the first reaction gas 17 into the reaction chamber 300 for 90 seconds, wherein a part of the first reaction gas 17 is attached to the surface of the lower electrode bracket group 7; the first reaction gas 17 in this embodiment includes an oxygen source precursor, specifically including one or more of steam, oxygen, ozone, nitrous oxide, or vaporized hydrogen peroxide; a first vacuum is applied to the first reaction gas 17 for 20 seconds, and a first cleaning gas is introduced into the reaction chamber 300 for 20 seconds; repeating the step once;
introducing a second reaction gas 18, and introducing the second reaction gas 18 into the reaction chamber 300 for 60 seconds, wherein the second reaction gas 18 reacts with the first reaction gas 17 attached to the surface of the lower electrode holder set 7 to form a first layer of thin film 8; the second reactant gas 18 in this embodiment includes C 11 H 22 N 3 Zr；
Performing primary vacuumizing on the second reaction gas 18 for 20 seconds, and introducing a second cleaning gas into the reaction chamber 300 for 20 seconds; repeating the step three times;
the time required for one rotation of the susceptor 11 is 30s, that is, the time required for introducing the first cleaning gas is not an integer multiple of the time required for one rotation of the susceptor 11. After the implementation, the thickness distribution of the film formed on the surface of the lower electrode bracket set 7 is thicker in the middle and on two sides and is expressed as a first thickness 12; the thickness of the thin film in the area between the center position and the two sides is thinner and is the second thickness 13; as shown in fig. 14.
By combining example 1 with comparative example 1, as shown in tables 1 and 2, it can be obtained that when the time taken to introduce the first cleaning gas is a non-integer multiple of the time taken to rotate the susceptor 11 once, the residual byproducts in the local area of the lower electrode support set 7 cause the deposition thickness of the subsequent dielectric layer to be thinner, and the leakage current loss of the capacitor is increased. Meanwhile, the whole process of comparative example 1 takes longer time than that of example 1, which is disadvantageous in improving production efficiency. Meanwhile, as shown in fig. 16, the thickness distribution of the film prepared in example 1 was uniform as compared with that of the film prepared in comparative example 1.
Table 1 comparison of time parameters of example 1 and comparative example 1 when the first cleaning gas was introduced
Figure BDA0001685485960000091
Figure BDA0001685485960000101
Table 2 comparative table of example 1 and comparative example 1 taken together
Figure BDA0001685485960000102
In addition, compared with comparative example 1, in example 1, the number of circulating operations from the first vacuuming treatment to the introduction of the first cleaning gas is increased, so that residual byproducts in the reaction chamber 300 caused by the double sprayer are effectively reduced, subsequent ozone deposition is prevented from being blocked, and dust pollution can be reduced;
reducing the operation times from the second vacuumizing treatment to the second cleaning gas, so that more ozone gas is remained in the reaction chamber 300, more OH-bonding can be generated, and the subsequent dielectric layer chemical adsorption reaction and mass deposition are facilitated;
the total number of the circulation from the first vacuumizing treatment to the first cleaning gas and the circulation from the second vacuumizing treatment to the second cleaning gas is reduced, so that the production time can be reduced, and the productivity can be effectively improved.
Preferably, the first cleaning gas includes one of inert gas and nitrogen, such as nitrogen, neon, or argon, etc.; the second cleaning gas includes one of an inert gas and nitrogen, such as nitrogen, neon, or argon.
In order to control the thickness of the film, the above method may further include introducing a third reaction gas: introducing a third reactive gas into the reaction chamber 300, the third reactive gas being partially adhered to the surface of the first thin film 8; the third reaction gas comprises C 11 H 22 N 3 Zr；
Introducing a third cleaning gas: performing fifth vacuumizing treatment on the reaction chamber 300, introducing the third cleaning gas into the reaction chamber 300 for the first time, performing sixth vacuumizing treatment on the reaction chamber 300, introducing the third cleaning gas into the reaction chamber 300 for the second time, performing seventh vacuumizing treatment on the reaction chamber 300, and introducing the third cleaning gas into the reaction chamber 300 for the third time to discharge the third reaction gas floating and remaining in the reaction chamber 300;
the time for introducing the third cleaning gas is an integral multiple of the time for rotating the bearing table 11 for one circle; the third cleaning gas is nitrogen;
introducing a fourth reaction gas: introducing the fourth reaction gas into the reaction chamber 300, wherein the fourth reaction gas reacts with the third reaction gas attached to the surface of the first thin film 8 to form a second thin film; the fourth reactant gas comprises one or more of steam, oxygen, ozone, nitrous oxide, or vaporized hydrogen peroxide;
introducing a fourth cleaning gas: performing eighth vacuumizing treatment on the reaction chamber 300, and introducing the fourth cleaning gas into the reaction chamber 300 to discharge the fourth reaction gas suspended and remained in the reaction chamber 300 and free byproducts of the reaction of the third reaction gas and the fourth reaction gas; the fourth cleaning gas is introduced for an integer multiple of the rotation time of the carrying table 11; the fourth cleaning gas is nitrogen.
At this time, the second film and the first film are the same film. Of course, the second layer of film and the first layer of film may be different films, and when the second layer of film and the first layer of film are different films, the third reaction gas may include titanium tetrachloride, and the fourth reaction gas may be ammonia; the third cleaning gas and the fourth gas can be nitrogen or argon.
And repeatedly introducing a third reaction gas, a third cleaning gas, a fourth reaction gas and a fourth cleaning gas for several times, thereby ensuring the uniformity of the thickness of the deposited film. The specific steps are as follows: and further comprises introducing a fifth reaction gas, wherein the fifth reaction gas is partially adhered to the surface of the second layer of film, and the fifth reaction gas is introduced into the reaction chamber 300;
introducing a fifth cleaning gas: performing a ninth vacuum pumping treatment on the reaction chamber 300, introducing the fifth cleaning gas into the reaction chamber 300 for the first time, performing a tenth vacuum pumping treatment on the reaction chamber 300, introducing the fifth cleaning gas into the reaction chamber 300 for the second time, performing an eleventh vacuum pumping treatment on the reaction chamber 300, and introducing the fifth cleaning gas into the reaction chamber 300 for the third time, so as to discharge the fifth reaction gas floating and remaining in the reaction chamber 300; the fifth reaction gas comprises an oxygen source precursor; preferably, the fifth reactant gas comprises one or more of steam, oxygen, ozone, nitrous oxide, or vaporized hydrogen peroxide;
the time for introducing the fifth cleaning gas is an integral multiple of the time for rotating the bearing table 11 for one circle; the fifth cleaning gas is nitrogen;
and (3) introducing a sixth reaction gas: introducing the sixth reaction gas into the reaction chamber 300, wherein the sixth reaction gas reacts with the fifth reaction gas attached to the surface of the second thin film to form a third thin film; the sixth reaction gas includes C 11 H 22 N 3 Zr and does not chemically react with the fifth cleaning gas;
introducing a sixth cleaning gas: performing a twelfth vacuum pumping treatment on the reaction chamber 300, and introducing the sixth cleaning gas into the reaction chamber 300 to discharge the sixth reaction gas suspended and remained in the reaction chamber 300 and free byproducts of the reaction of the fifth reaction gas and the sixth reaction gas; preferably, the sixth cleaning gas is introduced for an integer multiple of one rotation time of the susceptor 11; the sixth cleaning gas is nitrogen.
The foregoing is a description of embodiments of the invention, which are specific and detailed, but are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention.

Claims (12)

1. An atomic layer deposition method, comprising the steps of:
s1, providing a reaction chamber, wherein a rotatable bearing table is arranged in the reaction chamber; the wafer provided with the lower electrode bracket group is loaded on the bearing table;
s2, introducing a first reaction gas into the reaction chamber, wherein a part of the first reaction gas is attached to the surface of the lower electrode bracket group;
s3, cleaning a first chamber, namely performing first vacuumizing treatment on the reaction chamber, and then introducing first cleaning gas into the reaction chamber, wherein the circulation operation from the first vacuumizing treatment to the introduction of the first cleaning gas is performed for two or more times to discharge the first reaction gas suspended and remained in the reaction chamber;
s4, introducing a second reaction gas into the reaction chamber, wherein the second reaction gas reacts with the first reaction gas attached to the surface of the lower electrode bracket set so as to form a first layer of film on the surface of the lower electrode bracket set;
s5, cleaning a second chamber, namely performing second vacuumizing treatment on the reaction chamber, and then introducing the second cleaning gas into the reaction chamber to discharge second reaction gas suspended and remained in the reaction chamber and free byproducts of the reaction of the first reaction gas and the second reaction gas;
and in the processes of the first vacuumizing treatment and the introduction of the first cleaning gas, the bearing table keeps rotating, the time for introducing the first cleaning gas meets the integral multiple relation of the time for rotating the bearing table for one circle, and the number of circulating operation times from the first vacuumizing treatment to the introduction of the first cleaning gas is larger than that from the second vacuumizing treatment to the introduction of the second cleaning gas.
2. The atomic layer deposition method according to claim 1, wherein the first reactive gas comprises an oxygen source precursor and the second reactive gas comprises C 11 H 22 N 3 Zr, and does not chemically react with the first cleaning gas.
3. The atomic layer deposition method according to claim 1, wherein the first cleaning gas and the second cleaning gas include one of an inert gas and nitrogen gas.
4. The method of claim 1, wherein the time for the first vacuum process also satisfies an integer multiple of the time for one rotation of the susceptor.
5. The atomic layer deposition method according to claim 1, wherein the lower electrode holder set includes a lower support layer, an intermediate support layer, an upper support layer, and a lower electrode body; the lower support layer, the middle support layer and the upper support layer support the bottom, the middle and the top of the lower electrode body, respectively.
6. The atomic layer deposition method according to claim 1, wherein the materials of the lower support layer, the intermediate support layer and the upper support layer comprise silicon nitride; the material of the lower electrode body comprises titanium nitride.
7. An atomic layer deposition method according to claim 1, wherein,
further comprises: s6, introducing a third reaction gas into the reaction chamber, wherein the third reaction gas is partially attached to the surface of the first layer of film;
s7, cleaning a third chamber, namely performing third vacuumizing treatment on the reaction chamber, and then introducing third cleaning gas into the reaction chamber, wherein the circulation operation from the third vacuumizing treatment to the introduction of the third cleaning gas is performed for two or more times so as to discharge the third reaction gas floating in the reaction chamber;
s8, introducing the fourth reaction gas into the reaction chamber, wherein the fourth reaction gas reacts with the third reaction gas attached to the surface of the first layer of film to form a second layer of film;
s9, cleaning a fourth chamber, namely performing fourth vacuumizing treatment on the reaction chamber, and then introducing the fourth cleaning gas into the reaction chamber to discharge fourth reaction gas suspended and remained in the reaction chamber and free byproducts of the reaction of the third reaction gas and the fourth reaction gas;
and in the third vacuumizing treatment and the third cleaning gas introducing process, the bearing table keeps rotating, the time for introducing the third cleaning gas meets the integral multiple relation of the time for rotating the bearing table for one circle, and the number of circulating operation times from the third vacuumizing treatment to the third cleaning gas is larger than the number of operation times from the fourth vacuumizing treatment to the fourth cleaning gas.
8. The atomic layer deposition method according to claim 7, wherein the third cleaning gas and the fourth cleaning gas comprise nitrogen.
9. An atomic layer deposition method according to claim 7, wherein,
s10, introducing a fifth reaction gas into the reaction chamber, wherein the fifth reaction gas is partially adhered to the surface of the second layer of film;
s11, cleaning a fifth chamber, namely performing fifth vacuumizing treatment on the reaction chamber, and then introducing fifth cleaning gas into the reaction chamber, wherein the circulation operation from the fifth vacuumizing treatment to the introduction of the fifth cleaning gas is performed for two or more times so as to discharge the fifth reaction gas floating and remaining in the reaction chamber;
s12, introducing the sixth reaction gas into the reaction chamber, wherein the sixth reaction gas reacts with the fifth reaction gas attached to the surface of the second layer of film to form a third layer of film;
s13, cleaning a sixth chamber, namely performing a sixth vacuumizing treatment on the reaction chamber, and then introducing the sixth cleaning gas into the reaction chamber to discharge the sixth reaction gas suspended and remained in the reaction chamber and free byproducts of the reaction of the fifth reaction gas and the sixth reaction gas.
10. The atomic layer deposition method according to claim 9, wherein the fifth cleaning gas and the sixth cleaning gas include one of an inert gas and nitrogen gas.
11. The atomic layer deposition method according to claim 9, wherein the fifth reactive gas comprises an oxygen source precursor, and the sixth reactive gas comprises C 11 H 22 N 3 Zr, and does not chemically react with the fifth cleaning gas.
12. An atomic layer deposition method according to any one of claims 1 to 11, wherein the second reactive gas is introduced into the reaction chamber using a dual atomizer.
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