CN113394075A - high-K dielectric layer repairing method - Google Patents

high-K dielectric layer repairing method Download PDF

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Publication number
CN113394075A
CN113394075A CN202110504592.0A CN202110504592A CN113394075A CN 113394075 A CN113394075 A CN 113394075A CN 202110504592 A CN202110504592 A CN 202110504592A CN 113394075 A CN113394075 A CN 113394075A
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dielectric layer
repairing
range
temperature
plasma oxidation
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姜兰
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Shanghai Huali Integrated Circuit Manufacturing Co Ltd
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Shanghai Huali Integrated Circuit Manufacturing Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
    • H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
    • H01L21/02181—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing hafnium, e.g. HfO2
    • 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
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
    • 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
    • C23C16/22—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 deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/405—Oxides of refractory metals or yttrium
    • 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]
    • C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
    • 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
    • C23C16/56—After-treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H01L21/0228—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD

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Abstract

The invention discloses a high K dielectric layer repairing method, which comprises the following steps: providing a substrate; growing an ultrathin interface layer on a substrate; depositing a high-K dielectric layer on the ultrathin interface layer; repairing the high-K dielectric layer by adopting plasma oxidation at a preset temperature; the preset temperature is less than 500 ℃. Compared with the traditional high-temperature rapid thermal annealing process, the low-temperature plasma oxidation method can avoid the aggravation of the thermal movement of the internal molecules of the dielectric layer at the low temperature and avoid the thickening of the interface layer caused by the oxygen entering the interface. The interface morphology meets the design requirements, and the influence on the device performance is avoided; on the other hand, H in a low temperature environmentfO2The amorphous state is maintained and no crystallization occurs. The invention can not only treat HfO2Can be sufficiently repaired while preventing the interface layer from becoming thick and HfO2Crystallization occurs, thereby improving device performance.

Description

high-K dielectric layer repairing method
Technical Field
The invention relates to the field of integrated circuit manufacturing, in particular to a high-K dielectric layer repairing method.
Background
With the continuous reduction of the device size according to the requirement of the Er's law, the thickness of the gate dielectric is continuously reduced, but the leakage current of the gate is increased. In order to solve the problem of grid leakage, a high-K medium is urgently needed to replace SiO2SiON, which can reduce equivalent silicon dioxideThe insulation thickness (EOT) is simultaneously larger than the physical thickness of a gate dielectric, so that the gate leakage current is reduced. Currently, high-K dielectric materials hafnium oxide (HfO)2) Is substituted for SiO2One of the preferred choices of/SiON.
high-K dielectric layer HfO2Formed mainly by atomic layer deposition due to HfO2The layer has oxygen vacancy defects and is subsequently repaired by a high temperature post-deposition annealing treatment. The oxygen vacancy in the dielectric layer can be filled by deposition annealing after high temperature, and the defects in the dielectric layer are reduced. However, due to the high post-deposition annealing temperature (650 ℃ or higher), on one hand, the thermal movement of some molecules in the dielectric layer is increased, which leads to the repair of HfO by oxygen in the external environment2Oxygen vacancies can enter an interface, so that the thickness of the interface layer (Interfacial layer) is increased, the interface state is deteriorated, and the performance of the device is influenced; on the other hand, HfO in high temperature environment2It is transformed from the deposited amorphous state to a monoclinic phase, and crystallization occurs, resulting in an increase in leakage current.
Disclosure of Invention
In this summary, a series of simplified form concepts are introduced that are simplifications of the prior art in this field, which will be described in further detail in the detailed description. This summary of the invention is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used as an aid in determining the scope of the claimed subject matter.
The technical problem to be solved by the invention is to provide a method for avoiding the thickening of an interface layer and HfO2A method for repairing a high-K dielectric layer with crystallization.
In order to solve the technical problem, the high-K dielectric layer repairing method provided by the invention comprises the following steps:
s1, providing a substrate;
s2, growing an ultrathin interface layer on the substrate;
s3, depositing a high-K dielectric layer on the ultrathin interface layer;
s4, repairing the high-K dielectric layer by adopting plasma oxidation at a preset temperature;
wherein the preset temperature is less than 500 ℃.
Optionally, the method for repairing the high-K dielectric layer is further improved, and the substrate is a silicon substrate.
Optionally, the method for repairing the high-K dielectric layer is further improved, and the thickness of the ultrathin interface layer ranges from 5 angstroms to 10 angstroms.
Optionally, the method for repairing the high-K dielectric layer is further improved, and the ultrathin interface layer is formed by an in-situ steam oxidation method or a chemical oxidation method.
Optionally, the method for repairing the high-K dielectric layer is further improved, wherein the high-K dielectric layer is formed by an atomic layer deposition method, and a precursor used for deposition is hafnium tetrachloride.
Optionally, the method for repairing the high-K dielectric layer is further improved, wherein the high-K dielectric layer is hafnium oxide.
Optionally, the method for repairing the high-K dielectric layer is further improved, and the thickness of the high-K dielectric layer ranges from 10 angstroms to 40 angstroms.
Optionally, the method for repairing the high-K dielectric layer is further improved, and the thickness of the high-K dielectric layer is 20 angstroms.
Optionally, the method for repairing a high-K dielectric layer is further improved, and when step S4 is implemented, the plasma oxidation conditions include:
the temperature range is 200-400 ℃, the time range is 10-300 seconds, the pressure range is 10-30 mTorr, the plasma oxidation operation mode is a continuous mode, the radio frequency power range is 150-1900 watts, the oxygen flow range is 150-300 ml/min, and the proportion range of oxygen and helium is 100-10%.
Optionally, the high-K dielectric layer repairing method is further improved, and the plasma oxidation condition is
Temperature 400 ℃, time range 10 seconds, pressure range 20 mtorr, plasma oxidation operation mode continuous mode, radio frequency power range 150 watts, oxygen flow range 300 ml/min, oxygen and helium ratio range 50%: 50 percent.
Compared with the traditional high-temperature rapid thermal annealing process, the invention carries out low-temperature Plasma oxidation (DPO) on the HfO of the high-K dielectric layer2The low-temperature plasma oxidation method has the advantages of low temperature, accurate control of oxygen atom content and the like. The low temperature can avoid the aggravation of the thermal movement of the molecules in the dielectric layer and the thickness increase of the interface layer caused by the oxygen entering the interface. The interface morphology meets the design requirements, and the influence on the device performance is avoided; on the other hand, HfO in a low temperature environment2An amorphous state is maintained and crystallization does not occur, so that a leakage current can be maintained. The invention can not only treat HfO2Can be sufficiently repaired while preventing the interface layer from becoming thick and HfO2Crystallization occurs, thereby improving device performance.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention, are incorporated in and constitute a part of this specification. The drawings are not necessarily to scale, however, and may not be intended to accurately reflect the precise structural or performance characteristics of any given embodiment, and should not be construed as limiting or restricting the scope of values or properties encompassed by exemplary embodiments in accordance with the invention. The invention will be described in further detail with reference to the following detailed description and accompanying drawings:
FIG. 1 is a schematic flow diagram of the present invention.
FIG. 2 is a first schematic diagram of the present invention.
FIG. 3 is a second schematic diagram of the present invention.
FIG. 4 is a plasma oxidation process for repairing HfO2Schematic representation.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and technical effects of the present invention will be fully apparent to those skilled in the art from the disclosure in the specification. The invention is capable of other embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the general spirit of the invention. It is to be noted that the features in the following embodiments and examples may be combined with each other without conflict. The following exemplary embodiments of the present invention may be embodied in many different forms and should not be construed as limited to the specific embodiments set forth herein. It is to be understood that these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the technical solutions of these exemplary embodiments to those skilled in the art.
A first embodiment;
as shown in fig. 1, the present invention provides a method for repairing a high K dielectric layer, comprising the following steps:
s1, providing a substrate;
s2, growing an ultrathin interface layer on the substrate;
s3, depositing a high-K dielectric layer on the ultrathin interface layer;
s4, repairing the high-K dielectric layer by adopting plasma oxidation at a preset temperature;
wherein the preset temperature is less than 500 ℃.
A second embodiment;
with continued reference to fig. 1, the present invention provides a method for repairing a high-K dielectric layer, comprising the following steps:
s1, providing a silicon substrate;
s2, forming an ultrathin interface layer with the growth thickness of 5-10 angstroms on the substrate by adopting an in-situ steam oxidation method or a chemical oxidation method;
s3, forming a high-K dielectric layer with the thickness ranging from 10 angstroms to 40 angstroms on the ultrathin interface layer by an atomic layer deposition method, wherein a precursor used for deposition is hafnium tetrachloride, and the high-K dielectric layer is hafnium oxide;
s4, repairing the high-K dielectric layer by adopting plasma oxidation at a preset temperature;
wherein the preset temperature is less than 500 ℃.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular is intended to include the plural unless the context clearly dictates otherwise. It will be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
A third embodiment;
with continued reference to fig. 1, the present invention provides a method for repairing a high-K dielectric layer, comprising the following steps:
s1, providing a silicon substrate;
s2, forming an ultrathin interface layer with a growth thickness of 5-10 angstroms on the substrate by an in-situ steam oxidation method or a chemical oxidation method as shown in FIG. 2;
s3, as shown in FIG. 3, forming a high-K dielectric layer with a thickness ranging from 10 angstroms to 40 angstroms on the ultrathin interface layer by an atomic layer deposition method, wherein a precursor used for deposition is hafnium tetrachloride, and the high-K dielectric layer is hafnium oxide;
s4, referring to fig. 4, the plasma oxidation conditions for repairing the high-K dielectric layer are as follows:
the temperature range is 200-400 ℃, the time range is 10-300 seconds, the pressure range is 10-30 mTorr, the plasma oxidation operation mode is a continuous mode, the radio frequency power range is 150-1900 watts, the oxygen flow range is 150-300 ml/min, and the proportion range of oxygen and helium is 100-10%.
A fourth embodiment;
with continued reference to fig. 1, the present invention provides a method for repairing a high-K dielectric layer, comprising the following steps:
s1, providing a silicon substrate;
s2, forming an ultrathin interface layer with the growth thickness of 5-10 angstroms on the substrate by adopting an in-situ steam oxidation method or a chemical oxidation method;
s3, forming a high-K dielectric layer with the thickness ranging from 10 angstroms to 40 angstroms on the ultrathin interface layer by an atomic layer deposition method, wherein a precursor used for deposition is hafnium tetrachloride, and the high-K dielectric layer is hafnium oxide;
s4, repairing the high-K dielectric layer under the following plasma oxidation conditions:
temperature 400 ℃, time range 10 seconds, pressure range 20 mtorr, plasma oxidation operation mode continuous mode, radio frequency power range 150 watts, oxygen flow range 300 ml/min, oxygen and helium ratio range 50%: 50 percent.
Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
The present invention has been described in detail with reference to the specific embodiments and examples, but these are not intended to limit the present invention. Many variations and modifications may be made by one of ordinary skill in the art without departing from the principles of the present invention, which should also be considered as within the scope of the present invention.

Claims (10)

1. A high K dielectric layer repairing method is characterized by comprising the following steps:
s1, providing a substrate;
s2, growing an ultrathin interface layer on the substrate;
s3, depositing a high-K dielectric layer on the ultrathin interface layer;
s4, repairing the high-K dielectric layer by adopting plasma oxidation at a preset temperature;
wherein the preset temperature is less than 500 ℃.
2. The method for repairing a high-K dielectric layer according to claim 1, wherein: the substrate is a silicon substrate.
3. The method for repairing a high-K dielectric layer according to claim 1, wherein: the thickness range of the ultrathin interface layer is 5-10 angstroms.
4. The method for repairing a high-K dielectric layer according to claim 1, wherein: the ultrathin interface layer is formed by adopting an in-situ steam oxidation method or a chemical oxidation method.
5. The method for repairing a high-K dielectric layer according to claim 1, wherein: the high-K dielectric layer is formed by adopting an atomic layer deposition method, and a precursor adopted by deposition is hafnium tetrachloride.
6. The method for repairing a high-K dielectric layer according to claim 1, wherein: the high-K dielectric layer is hafnium oxide.
7. The method for repairing a high-K dielectric layer according to claim 1, wherein: the thickness range of the high-K dielectric layer is 10-40 angstroms.
8. The method for repairing a high-K dielectric layer according to claim 1, wherein: the thickness of the high-K dielectric layer is 20 angstroms.
9. The method for repairing a high-K dielectric layer according to any one of claims 1 to 8, wherein the plasma oxidation conditions include:
the temperature range is 200-400 ℃, the time range is 10-300 seconds, the pressure range is 10-30 mTorr, the plasma oxidation operation mode is a continuous mode, the radio frequency power range is 150-1900 watts, the oxygen flow range is 150-300 ml/min, and the proportion range of oxygen and helium is 100-10%.
10. The method for repairing a high-K dielectric layer of claim 9, wherein the plasma oxidation conditions are
Temperature 400 ℃, time range 10 seconds, pressure range 20 mtorr, plasma oxidation operation mode continuous mode, radio frequency power range 150 watts, oxygen flow range 300 ml/min, oxygen and helium ratio range 50%: 50 percent.
CN202110504592.0A 2021-05-10 2021-05-10 high-K dielectric layer repairing method Pending CN113394075A (en)

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CN102664147A (en) * 2012-05-14 2012-09-12 中国科学院上海微系统与信息技术研究所 Method for preparing Hf-based high-K gate dielectric film on GaAs substrate
CN103956325A (en) * 2014-05-19 2014-07-30 青岛大学 Multi-layer composite oxide high-k dielectric film transistor manufacturing method
CN104103509A (en) * 2013-04-10 2014-10-15 中芯国际集成电路制造(上海)有限公司 Formation method of interfacial layer and formation method of metal gate transistor
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