CN108987376A - A kind of anti-Cu diffusion barrier material of low-resistivity manganese oxygen nitrogen - Google Patents
A kind of anti-Cu diffusion barrier material of low-resistivity manganese oxygen nitrogen Download PDFInfo
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- CN108987376A CN108987376A CN201810660178.7A CN201810660178A CN108987376A CN 108987376 A CN108987376 A CN 108987376A CN 201810660178 A CN201810660178 A CN 201810660178A CN 108987376 A CN108987376 A CN 108987376A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
- H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
- H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
- H01L23/53204—Conductive materials
- H01L23/53209—Conductive materials based on metals, e.g. alloys, metal silicides
- H01L23/53228—Conductive materials based on metals, e.g. alloys, metal silicides the principal metal being copper
- H01L23/53238—Additional layers associated with copper layers, e.g. adhesion, barrier, cladding layers
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0676—Oxynitrides
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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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
- C23C16/22—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
- C23C16/308—Oxynitrides
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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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/7685—Barrier, adhesion or liner layers the layer covering a conductive structure
Abstract
The invention discloses a kind of anti-Cu diffusion barrier material of low-resistivity manganese oxygen nitrogen, which is the film being made of tri- kinds of elements of Mn, O, N, wherein the ratio of each element are as follows: O atom content: 1 part；N atom content: 1.05 ~ 1.25 parts；Mn atom content: 2.45 ~ 3.11 parts, the atomicity content that the above atom content refers to.Manganese oxygen nitrogen barrier material provided by the invention has both the characteristics of high conductivity and highly resistance Cu diffusivity, can effectively stop the diffusion of Cu under conditions of annealing 30 minutes for 550 DEG C in the case where ~ 2.4 nm.The material can realize the control of resistivity of material by regulation atomic ratio, and can use easy to spread with the methods of the magnetron sputtered deposition technology, chemical vapour deposition technique and technique for atomic layer deposition of ic process compatibility preparation, simple process.
Description
Technical field
The invention belongs to integrated circuit Cu interconnection field, it is related to for anti-Cu diffusion barrier material in Cu interconnection technique,
The lower and adjustable anti-Cu diffusion barrier material of manganese oxygen nitrogen (Mn-O-N) more particularly to a kind of resistivity.
Background technique
In IC manufacturing field, in order to constantly improve the performance of chip, the characteristic size of integrated circuit is continuous
Reduction, while device architecture and material are constantly being innovated, such as: the fin-shaped knot proposed to reduce device size as far as possible
Structure field effect transistor (FinFET), for enhancing grid control ability high dielectric constant (high-k) material that introduces and
Metal gate material.Equally, in integrated circuit interconnection field, in order to reduce resistance caused by interconnection line and interconnection line and medium and
Capacitor (RC) delay, introduce Cu and low-k (low-k) material as interconnection line and medium, and in order to prevent Cu to
It is spread in low-k material, the Ta/TaN material that insertion is grown using physical gas phase deposition technology (PVD) between Cu and low-k
As barrier layer, while Ta/TaN can also play the role of enhancing interlayer adhesion.
However, there are many poorly conductive of the electric conductivity ratio Cu of barrier material, since interconnection dimensions are with circuit feature size
Constantly reduce, the thickness on barrier layer must also reduce with holding circuit performance therewith.When the groove width contracting interconnected in circuit
When as low as 20 ~ 30 nm, the thickness of PVD deposition Ta/TaN barrier bi-layer has been approached its limit, and is difficult to realize in the trench
Even deposit.
Therefore, many new barrier deposition schemes and novel stop material system are suggested, such as: Co base barrier layer, the resistance of W base
Barrier, Ru base barrier layer and Mn base barrier layer etc..Wherein, in Mn base barrier layer, MnN be can be enhanced between Cu and low-k medium
Adhesiveness, and Mn can with low-k medium interface react generate one layer of ultra-thin MnSixOyFilm, to keep enough
Big groove space, and this layer of MnSixOyIt is smaller on the influence of the dielectric constant of low-k medium, thus Mn base barrier layer is interconnected in Cu
Extensive concern has been obtained in the application on barrier layer.
But in traditional Mn base barrier layer formed manganese silicon oxide compound barrier layer while along with low-k medium
Reaction, this, which means that, will consume a part of medium.Meanwhile the MnSi of generationxOyThe electric conductivity of compound is poor, generally
For insulator, this just undesirably increases interconnection resistance.
Summary of the invention
Present invention aim to address the drawbacks described above of existing Mn sill, a kind of conduction, not lossy medium material are provided
Material or the weaker and anti-preferable barrier material of Cu diffusion with dielectric material reactivity, contain Mn, O simultaneously
With tri- kinds of elements of N, there is high conductivity, and the barrier material is mutually compatible with integrated circuit interconnection technique, preparation method is simple
It is easy, there is good application prospect.
In order to achieve the above object, the present invention provides a kind of anti-Cu diffusion barrier material of low-resistivity manganese oxygen nitrogen, the resistance
Barrier material is the film being made of tri- kinds of elements of Mn, O, N, wherein the ratio of each element are as follows:
O atom content: 1 part；
N atom content: 1.05 ~ 1.25 parts；
Mn atom content: 2.45 ~ 3.11 parts；
The atomicity content that the above atom content refers to.
Preferably, the barrier material can be grown by ALD method, the ratio of each element passes through control growth temperature, Mn
The intake in source, the source N and the source O is adjusted.If, can be by controlling the gas flow containing O and containing by the method for PVD
The gas flow of N adjusts the content of O and N inside film.
Preferably, the source Mn selects metallorganic or target containing Mn.
Preferably, the source Mn selects MnCp2、Mn(EtCp)2, metal Mn target, MnO target and MnN target
Preferably, the source N selects the gas containing N element.
Preferably, the source N selects NH3、N2O or N2。
Preferably, the source O selects the gas containing O element.
Preferably, the source O selects O2、H2O steam or O3。
Preferably, the barrier material passes through one of magnetron sputtering, chemical vapor deposition or atomic layer deposition method
Preparation.
Preferably, the barrier material is prepared using Atomic layer deposition method, by adjust substrate or reaction chamber temperature come
Control the element composition of film.
Preferably, heating temperature selects 100 ~ 300 DEG C, preferably 200-300 DEG C.
Heretofore described " low-resistivity " refers to the MnSi common relative to traditionxOyManganese and oxygen compound Mn base stops
It is lower for the resistivity of layer.
Compared with traditional Mn base barrier material, the anti-Cu diffusion barrier material of low-resistivity manganese oxygen nitrogen provided by the invention
With following significant progress:
1) resistivity is greatly reduced, and has preferable conductive characteristic；
2) not lossy medium material or to dielectric material be lost it is less；
3) present invention contains O element and N element, while adhesiveness with higher and preferable barrier properties simultaneously；
4) for the barrier material that the present invention is grown in the case where very thin thickness, such as ~ 2.4 nm can have excellent anti-Cu
Diffusion property can effectively reduce interconnection delay in conjunction with preferable electric conductivity.
Specific embodiment
The present invention provides a kind of anti-Cu diffusion barrier material of low-resistivity manganese oxygen nitrogen, the barrier material be by Mn,
O, the film of tri- kinds of elements of N composition, wherein the atomic ratio of each element are as follows:
O atom content: 1 part；
N atom content: 1.05 ~ 1.25 parts；
Mn atom content: 2.45 ~ 3.11 parts.
The technological parameter when ratio of each element is by control film growth in the barrier material is adjusted.
Specifically, ALD method realizes the adjustment of element ratio by control growth temperature, can also pass through the control source Mn, the source N and O
The intake in source realizes the regulation of element different in film；The method of PVD can be by controlling sputtering power, gas containing O
The flow of body, the flow of the gas containing N and operating pressure adjust the content of O and N inside film.The material can pass through regulation
(during practical growth, the crystallinity of resistivity and film also has very high point for the control of atomic ratio realization resistivity of material
System, is typically embodied as that crystallinity is higher, and resistivity is lower.), and can use the magnetron sputtering with ic process compatibility
The preparation of the methods of deposition technique, chemical vapour deposition technique and technique for atomic layer deposition, simple process are easy to spread.
The source Mn selects metallorganic or target containing Mn；It is preferred that MnCp2、Mn(EtCp)2, metal Mn target
Material, MnO target and MnN target (wherein MnO and MnN only indicates to be made of which kind element, does not indicate the practical composition of target).
The source N selects the gas containing N element, preferably NH3、N2O or N2。
The source O selects the gas containing O element, preferably O2、H2O steam or O3。
Barrier material of the invention can be prepared by a variety of methods respectively, such as magnetron sputtering, chemical vapor deposition or original
Sublayer deposition.
The following further describes the technical solution of the present invention with reference to embodiments.
A specific embodiment of the invention is as follows:
Firstly, in order to obtain Mn-O-N barrier material proposed by the present invention, the present embodiment use technique for atomic layer deposition as
The preparation method of Mn-O-N material is selected Mn (EtCp)2As the source Mn, NH3Plasma is as the source N, O2Or H2O steam is as O
Source.For example, being first passed through the source Mn, using N2The extra source Mn is purged, then the source N is passed through simultaneously and the mixture in the source O is reacted.
Finally use N2Byproduct of reaction purging is clean, generate Mn-O-N barrier material.
Secondly, the present invention controls the relative amount of Mn, O and N each element in film by the way of changing underlayer temperature,
Obtain the Mn-O-N barrier film of four kinds of different components with a thickness of ~ 20 nm under different temperatures, and its internal each element
The resistivity of atomic ratio and film is as shown in table 1.
Table 1: the different atomic ratios of element and the resistivity of film in the Mn-O-N film grown at different temperatures
| Temperature (DEG C) | 225 | 250 | 275 | 300 |
| Mn:O:N | 2.45:1:1.25 | 2.74:1:1.21 | 3.11:1:1.22 | 2.84:1:1.05 |
| Resistivity (Ω cm) | 0.0340 | 0.0103 | 0.0065 | 0.0056 |
As can be seen that Mn-O-N barrier material manufactured in the present embodiment all has preferable electric conductivity, and resistivity is with life
The rising of long temperature and gradually decrease, and change along with element ratio in film.
In order to embody anti-Cu diffusion of the invention, table 2 give atomic ratio in the present embodiment be Mn:O:N=
The ultra-thin barrier layer of the different-thickness (2.4nm, 3.7nm) of 2.45:1:1.25 (is expressed as Mn2.45ON1.25) anti-Cu diffusivity
It can test result.Wherein, barrier properties test is using in N2/H2It anneals under -4% atmosphere and tests annealing front and back square resistance variations
Mode characterized.If square resistance with it is unannealed when it is suitable or lower when, illustrate that barrier film does not fail；If a certain
Under annealing temperature, apparent increase suddenly occurs for the square resistance of film, then illustrates that barrier film fails.
Table 2: the Mn of different-thickness2.45ON1.25The anti-Cu diffusion property on barrier layer
As shown in table 2, the ultra-thin barrier layer that the present invention is grown can bear 550 DEG C and anneal 30 points when with a thickness of ~ 2.4 nm
Clock is without failure (temperature when failure is more desirable, usually using 450 DEG C as minimum standard).When thickness increases to
When 3.7 nm, film can effectively can stop the diffusion of Cu under conditions of annealing 30 minutes for 600 DEG C.This illustrates life of the present invention
Long Mn-O-N barrier material not only has preferable electric conductivity, while being also equipped with excellent anti-Cu diffusion.
The above is only illustrated advantage of the invention as the embodiment of the present invention, not appoints to the present invention
What formal restriction.Although deposition method of the invention is described as technique for atomic layer deposition by the present embodiment, the present invention is simultaneously
Not limited to this, the preparation method of Mn-O-N barrier film of the present invention is equally applicable to magnetron sputtering technique and chemistry
Gas phase deposition technology etc..The present embodiment adjusts material internal constituent content using the mode of control underlayer temperature, but equally may be used also
With by the source Mn, the content in the source N and the source O or flow in modulated growth processes come the constituent content inside controlled material.
In conclusion Mn-O-N material proposed by the present invention can be by heavy with the magnetron sputtering of ic process compatibility
The methods of product technology, chemical vapour deposition technique and technique for atomic layer deposition realize the preparation of material.Wherein it is possible to pass through control
Technological parameter in made membrane growth course realizes the adjusting of constituent content in film.For example, Mn- is prepared using ALD technique
When O-N material film, the element that film can be controlled by adjusting underlayer temperature is formed.Preferably, heating temperature selection 100
~ 300 DEG C, more preferably, select 200 ~ 300 DEG C.Mn-O-N barrier film prepared by the present invention has preferable electric conductivity, chemistry
Stability and anti-Cu diffusion, deposition method is simple, is easy to be widely popularized.
It is discussed in detail although the contents of the present invention have passed through above preferred embodiment, but it should be appreciated that above-mentioned
Description is not considered as limitation of the present invention.After those skilled in the art have read above content, for of the invention
A variety of modifications and substitutions all will be apparent.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (9)
1. a kind of anti-Cu diffusion barrier material of low-resistivity manganese oxygen nitrogen, which is characterized in that the barrier material is by Mn, O, N
The film of three kinds of elements composition, wherein the ratio of each element atom are as follows:
O atom content: 1 part；
N atom content: 1.05 ~ 1.25 parts；
Mn atom content: 2.45 ~ 3.11 parts；
The atomicity content that the above atom content refers to.
2. the anti-Cu diffusion barrier material of low-resistivity manganese oxygen nitrogen according to claim 1, which is characterized in that the barrier layer
Material passes through any one method preparation in magnetron sputtering, chemical vapor deposition or atomic layer deposition.
3. the anti-Cu diffusion barrier material of low-resistivity manganese oxygen nitrogen according to claim 1 or 2, which is characterized in that the resistance
In barrier material the ratio of each element by growth temperature, the source Mn, the source N and the content in the source O in material preparation process or flow into
Row is adjusted.
4. the anti-Cu diffusion barrier material of low-resistivity manganese oxygen nitrogen according to claim 3, which is characterized in that the Mn
Source selects metallorganic or target containing Mn.
5. the anti-Cu diffusion barrier material of low-resistivity manganese oxygen nitrogen according to claim 4, which is characterized in that the Mn
Source selects MnCp2、Mn(EtCp)2, metal Mn target, any one in MnO target and MnN target.
6. the anti-Cu diffusion barrier material of low-resistivity manganese oxygen nitrogen according to claim 3, which is characterized in that the N
Source selects the gas containing N element or MnN target.
7. the anti-Cu diffusion barrier material of low-resistivity manganese oxygen nitrogen according to claim 6, which is characterized in that described contains
There is the gas selection NH of N element3、N2O or N2In any one.
8. the anti-Cu diffusion barrier material of low-resistivity manganese oxygen nitrogen according to claim 3, which is characterized in that the O
Source selects the gas containing O element or MnO target.
9. the anti-Cu diffusion barrier material of low-resistivity manganese oxygen nitrogen according to claim 8, which is characterized in that described contains
There is the gas selection O of O element2、H2O steam or O3In any one.
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| US5985759A (en) * | 1998-02-24 | 1999-11-16 | Applied Materials, Inc. | Oxygen enhancement of ion metal plasma (IMP) sputter deposited barrier layers |
| CN104465507A (en) * | 2014-12-26 | 2015-03-25 | 上海集成电路研发中心有限公司 | Copper interconnection forming method |
| CN104538346A (en) * | 2014-12-26 | 2015-04-22 | 上海集成电路研发中心有限公司 | Method for forming copper interconnection structure |
| CN104659050A (en) * | 2013-11-22 | 2015-05-27 | 台湾积体电路制造股份有限公司 | Top electrode blocking layer for RRAM device |
| US20150194384A1 (en) * | 2014-01-08 | 2015-07-09 | Applied Materials, Inc. | Cobalt Manganese Vapor Phase Deposition |
| US20160181150A1 (en) * | 2014-12-21 | 2016-06-23 | Applied Materials, Inc. | Precursors Of Manganese And Manganese-Based Compounds For Copper Diffusion Barrier Layers And Methods Of Use |
| US20180025989A1 (en) * | 2016-07-22 | 2018-01-25 | International Business Machines Corporation | Formation of liner and metal conductor |
-
2018
- 2018-06-25 CN CN201810660178.7A patent/CN108987376B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5985759A (en) * | 1998-02-24 | 1999-11-16 | Applied Materials, Inc. | Oxygen enhancement of ion metal plasma (IMP) sputter deposited barrier layers |
| CN104659050A (en) * | 2013-11-22 | 2015-05-27 | 台湾积体电路制造股份有限公司 | Top electrode blocking layer for RRAM device |
| US20150194384A1 (en) * | 2014-01-08 | 2015-07-09 | Applied Materials, Inc. | Cobalt Manganese Vapor Phase Deposition |
| US20160181150A1 (en) * | 2014-12-21 | 2016-06-23 | Applied Materials, Inc. | Precursors Of Manganese And Manganese-Based Compounds For Copper Diffusion Barrier Layers And Methods Of Use |
| CN104465507A (en) * | 2014-12-26 | 2015-03-25 | 上海集成电路研发中心有限公司 | Copper interconnection forming method |
| CN104538346A (en) * | 2014-12-26 | 2015-04-22 | 上海集成电路研发中心有限公司 | Method for forming copper interconnection structure |
| US20180025989A1 (en) * | 2016-07-22 | 2018-01-25 | International Business Machines Corporation | Formation of liner and metal conductor |
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