CN101345210A

CN101345210A - Process for forming continuous copper thin films via vapor deposition

Info

Publication number: CN101345210A
Application number: CNA2008102103331A
Authority: CN
Inventors: J·A·T·诺曼
Original assignee: Air Products and Chemicals Inc
Current assignee: Air Products and Chemicals Inc
Priority date: 2007-06-21
Filing date: 2008-06-20
Publication date: 2009-01-14

Abstract

A process for preparing a multi-layer substrate is described herein. In one embodiment, the process provides a multi-layer substrate comprising a first layer and a second layer where the process comprises the steps of providing the first layer comprising a barrier area and a copper area; and depositing the second layer comprising copper onto the first layer wherein the depositing provides the second layer comprising a first thickness ranging from about 20 Angstroms to about 2,000 Angstroms onto the barrier area and a second thickness ranging from about 0 Angstroms to about 1,000 Angstroms onto the copper area in the first layer wherein the first thickness is greater than the second thickness.

Description

Form the method for continuous copper thin films by vapour deposition

The cross reference of related application

Present patent application requires to be filed on June 21st, 2007, sequence number is 60/945,415, name is called the U.S. Provisional Patent Application of " method that forms continuous copper thin films by vapour deposition " and is filed on June 22nd, 2007, sequence number is 60/945,748, name is called the priority of the U.S. Provisional Patent Application of " method that forms continuous copper thin films by vapour deposition ", introduces the present invention for your guidance.

Background of invention

Semi-conductor industry is used metallic cross tie part, for example copper (Cu) and its alloy, in electronic device as, for example, in the current microprocessor.Metallic cross tie part, it can be the lametta that is embedded into, and has formed three-dimensional grid, relies on it, the thousands of transistor on the core of microprocessor can be communicated by letter (communicate) and be carried out complicated calculating.In the application of these and other because copper is excellent electric conductor, copper or its alloy surmounted other metals as, for example, aluminium and selected, thereby the high-speed interconnect of bigger current delivery ability is provided.

Interconnection path in the electronic device prepares with Damascus technics typically, whereby, lithographic patterning in dielectric is covered by the thin conforma layer of diffusion barrier material with groove etching and through hole.Diffusion impervious layer is typically united use with metal or copper layer, to stop reacting to each other or spread caused adverse effect by other parts of metal or copper layer and integrated circuit.Representational barrier material includes but not limited to, the carbide of titanium, tantalum, tungsten, chromium, molybdenum, zirconium, ruthenium, rhodium, iridium, vanadium and/or platinum and these materials, nitride, carbonitride, silicon carbide, silicon nitride and silicon-carbon nitride and comprise the alloy of same material.In some technology, for example, when such as the cross tie part cupric time, before with fine copper complete filling feature place, can cover diffusion impervious layer with " seed (seed) " or " triggering " thin layer of copper.Still in other cases, the Seed Layer of copper can be replaced with---perhaps except being used to (used inaddition to)---similar cobalt or similar conductive film " bonding " layer.Unnecessary copper then can remove by CMP (Chemical Mechanical Polishing) process.Since the feature place of minimum to be filled can less than 0.2 micron wide and surpass 1 micron dark, preferred use can be filled these feature places equably and do not stayed metallization technology that any its may cause finishing the space that the electricity in the product lost efficacy and come deposited copper Seed Layer (seed layer), copper adhesive layer and/or diffusion impervious layer.

Several different methods is ionized metal plasma (IMP) for example, physical vapor deposition (PVD), chemical vapor deposition (CVD), ald (ALD), plasma auxiliary chemical vapor deposition (PACVD), plasma enhanced chemical vapor deposition (PECVD) is electroplated, be used to deposit metal-containing layer with electroless plating, for example as copper, diffusion barrier and/or other layer.Among above-mentioned, CVD (Chemical Vapor Deposition) method, for example as the CVD and the ALD that use one or more Organometallic precursors, it may be the most promising method that forms metal and/or containing metal film, because these methods have the step coverage to the high aspect ratio structure excellence, with good through hole filling characteristic and better technology controlling and process to film thickness.In typical C VD technology, volatile steam that contains the Organometallic precursor of required metal is introduced into substrate surface, and chemical reaction takes place thereon, wherein contains thin film deposition as the metal of compound or pure element in substrate.Because carry with vapor form as volatile precursor to metal typical, vertical it can both arrive with surface level, so that equally distributed film to be provided.In typical A LD technology, volatile Organometallic precursor and reactant gas quilt alternately pulse are sent in the reactor, thereby the alternately monolayers of the restriction certainly of precursor/reactant are deposited in the substrate, wherein monolayers one react and form metal film or containing metal film, and this containing metal film is reduced to metal subsequently or uses with the form that is deposited.For example, if in ALD technology the Organometallic precursor of copper and suitable oxidant reaction, the cuprous oxide of gained or cupric oxide monolayer or multilayer can be used for semiconductor application or be reduced to metallic copper.

Gas-phase deposition for example allows people for example to control the thickness of gained film as time and temperature and precursor and reactant flow velocity and pressure by the control process conditions as CVD and ALD.Typically, for given process time unit, the chip temperature of higher pressure, higher precursor flow rate and Geng Gao can trend towards the film that provides thicker.For example, be established in case be used for given " process window " of CVD technology, the deposition rate of film can determine, and from this value, can be by depositing specific thickness for the suitable sedimentation time of this process choice.Be similar to CVD technology, in case the ALD process quilt is established, wherein with the growing metal film, the thickness of film can be determined by controlling employed total period in the substrate cocycle in the ALT pulse of Organometallic precursor and reactant gas.

For some application, for example as copper seed layer, desirable be that copper film forms thin as much as possible remains continuous in complete simultaneously.Since copper CVD technology trend towards by the copper metal core be formed in the substrate, it grows up at leisure to be in contact with one another at last to form continuous film up to these nuclear and carries out, the thickness of the minimum that can reach be subjected to copper examine coalescent point arrange.These nuclears are grown up by two processes.The first, deposit to stop, the copper atom on seed and/or adhesive layer surface migrates to and increases its size on the nuclear.The second, fresh copper atom is grown directly upon on the copper nuclear.Thereby, copper be deposited into diffusion barrier and/or adhesive layer and the copper that deposited on.

Similarly situation runs in copper CVD technology, thereby the alternately monolayers that rely on the volatile organic metal copper precursors of this technology to be sent into the restriction certainly of precursor/reactant in the reactor together with reactant gas by pulse alternately are deposited in the substrate, thereby monolayers one react and formed copper film.Like this, copper can be deposited into stop and/or adhesive layer and already present copper surface or Seed Layer on.List of references Zhengwen, Li, Antti, Rahtu, and Roy Gordon, Journal of the Electrochemical Society, 153 (111) C787-C794 (2006) provide the example of typical copper ALD technology, and wherein Fu Jia copper is deposited on the existing copper layer with the growth rate of the every circulation of 0.5 dust.Thereby, be deposited on stop or Seed Layer on any copper nuclear or bigger metallic copper regional area, can be by surperficial copper atom along the diffusion into the surface of barrier material to these nuclears or go up in the zone or be grown directly upon on these nuclears or the zone by fresh copper and grow up.In addition, some metal as the barrier layer commonly used for example can trend towards impelling copper to be agglomerated into discontinuous film as tantalum, be similar to water forms pearl on the surface of waxing form (referring to, for example, H.Kim, T.Koseki, T.Ohba, T.Ohta, Y.Kojima, H.Sato, Y.Shimogaki, Journal of the Electrochemical Society, 152 (*), G594-G600 (2005)).This discontinuous copper film may cause follow-up problem in the copper electroplating process.Thereby, stop, seed and/or adhesive layer---comprise on those layers that contain ruthenium, realize thin but still continuous copper film is challenging.

Therefore, need a kind of technology, wherein compared to before the copper that deposited, copper optionally be deposited on the thickness that reduces or quantity metallicly stop, on seed and/or the layer.

The invention summary

One aspect of the present invention provides a kind of technology, and it has satisfied at least a aforementioned need for preparing the substrate of the multilayer that comprises the ground floor and the second layer, and it comprises step: the ground floor that comprises ruthenium zone and copper zone is provided; Use at least a have following molecular formula (Ia), (Ib) and (II) in any precursor, the second layer that deposits cupric is to ground floor:

Wherein M is a copper;

Wherein X is selected from oxygen and NR ⁵

R wherein ¹, R ², R ³And R ⁵Be selected from hydrogen atom independently of one another; Halogen atom; Has formula NO ₂Nitro group; Has formula C _nH _2n+1Alkyl, wherein n is from 1 to 20 numeral; Has formula C _nH _xF _yFluoro-alkyl, wherein the result of (x+y) equals the result of (2n+1), and n is from 1 to 20 numeral; Has formula (R ⁶) ₃The alkyl silane of Si, wherein R ⁶Be alkyl, alkoxyl or acid amides independently of one another, it comprises 1 to 20 carbon atom; The aromatic group that comprises 6 to 12 carbon atoms; The aromatic radical that comprises 6 to 12 carbon atoms that alkyl replaces; The aromatic radical that comprises 6 to 12 carbon atoms that fluoro-alkyl replaces; The fluoro aromatic radical that comprises 6 to 12 carbon atoms; Has formula (CH ₂) _nO (C _mH _2m+1) ether, wherein n and m are from 1 to 20 numeral independently; Has formula (C _nH _xF _y) O (C _mH _wF _z) fluoro-ether, (x+y)=2n wherein, (w+z)=(2m+1), and n and m are from 1 to 20 numeral independently of one another; Has formula (R ⁷) ₃The silyl ether of SiO, wherein R ⁷Be the aromatic radical that comprises the alkyl of 1 to 20 carbon atom or comprise 6 to 12 carbon atoms independently of one another; The alkoxyl that comprises 1 to 20 carbon atom; With the acid amides that comprises 1 to 20 carbon atom;

R wherein ⁴Be to be selected to have formula C _nH _2n+1Alkyl, wherein n is from 1 to 20 numeral; Has formula C _nH _xF _yFluoro-alkyl, wherein the result of (x+y) equals the result of (2n+1), and n is from 1 to 20 numeral; Has formula (R ⁶) ₃The alkyl silane of Si, wherein R ⁶Be alkyl, alkoxyl or acid amides independently of one another, it comprises 1 to 20 carbon atom; The aromatic radical that comprises 6 to 12 carbon atoms; The aromatic radical that comprises the alkyl replacement of 6 to 12 carbon atoms; The aromatic radical that comprises the fluoro-alkyl replacement of 6 to 12 carbon atoms; The fluoro aromatic radical that comprises 6 to 12 carbon atoms; Has formula (CH ₂) _nO (C _mH _2m+1) ether, wherein n and m are from 1 to 20 numeral independently; Has formula (C _nH _xF _y) O (C _mH _wF _z) fluoro-ether, (x+y)=2n wherein, (w+z)=(2m+1), and n and m are from 1 to 20 numeral independently of one another; Has formula (R ⁷) ₃The silyl ether of SiO, wherein R ⁷Be the aromatic group that comprises the groups of 1 to 20 carbon atom or comprise 6 to 12 carbon atoms independently of one another; The alkoxyl that comprises 1 to 20 carbon atom; With the acid amides that comprises 1 to 20 carbon atom, and R wherein ⁴By hydrogen, atom or group cancellation are combined with L;

Wherein L is a ligand, is selected from the alkyl nitrile that comprises 2 to 20 carbon atoms; Has formula (R ⁸) ₃The silicyl nitrile of SiCN, wherein R ⁸Be alkyl, alkoxyl or acid amides independently of one another, it comprises 1 to 20 carbon atom; The alkynes that comprises 1 to 20 carbon atom; Has formula (R ⁹) ₃SiCCR ¹⁰Silicyl alkynes, wherein R ⁹Be alkyl, acid amides or alkoxyl independently of one another, it comprises 1 to 20 carbon atom, R ¹⁰Be hydrogen, alkoxyl, acid amides or the alkyl that comprises 1 to 20 carbon atom; Has formula (R ¹¹) ₃SiCCSi (R ¹¹) ₃Silicyl alkynes, R wherein ¹¹Be alkyl, acid amides or alkoxyl independently of one another, it comprises 1 to 20 carbon atom; The alkene, alkadienes or the alkatrienes that comprise 1 to 20 carbon atom; Has formula (R ¹²) ₃SiCR ¹³C (R ¹³) ₂Silicyl alkene, R wherein ¹²Be alkyl, alkoxyl, aromatic radical, vinyl or acid amides independently of one another, it comprises 1 to 20 carbon atom, and R ¹³Be hydrogen independently of one another, comprise the alkyl of 1 to 20 carbon atom or comprise the aromatic radical of 6 to 12 carbon atoms; Has formula (R ¹⁴) ₃SiCR ¹³CR ¹³Si (R ¹⁴) ₃Dimethyl silanyl alkene, R wherein ¹⁴Be alkyl, alkoxyl or acid amides independently of one another, it comprises 1 to 20 carbon atom, and R ¹³Be hydrogen atom or the alkyl that comprises 1 to 20 carbon atom independently of one another; The allene derivative that comprises 3 to 20 carbon atoms; Has formula (R ¹⁵) ₂CCC (R ¹⁵) ₂The allene derivative, R wherein ¹⁵Be hydrogen atom independently of one another or have formula (R ¹⁶) ₃The alkyl silane of Si, wherein R ¹⁶Be alkyl, acid amides or alkoxyl independently of one another, it comprises 1 to 20 carbon atom; Has formula R ¹⁷The alkyl isocyanide of NC, wherein R ¹⁷It is the alkyl that comprises 1 to 20 carbon atom; Has formula (R ¹⁸) ₃The silicyl isocyanide of SiNC, wherein R ¹⁸Be the alkyl that comprises 1 to 20 carbon atom independently of one another; With the aromatic radical that comprises 6 to 12 carbon atoms, and wherein L by making hydrogen, atom or group cancellation and R ⁴In conjunction with;

Wherein the organic metal key between M and L is selected from 2 singly-bounds and 1 singly-bound; With

Wherein deposition provide about 20 dusts of being included on the ruthenium zone to first thickness between about 2,000 dusts the second layer and provide and be included in the second layer of about 0 on the copper zone to second thickness of about 1,000 dust, and wherein first thickness greater than second thickness.In a special example, at least a portion of deposition step be have reducing agent in the presence of carry out.

On the other hand, preparation provided herein comprises the technology of substrate of the multilayer of the ground floor and the second layer, it comprises: ground floor is provided, it comprises barrier zones (barrier area) and copper zone, and this barrier zones comprises and is selected from least a in titanium, tantalum, tungsten, chromium, molybdenum, zirconium, ruthenium, rhodium, iridium, vanadium, platinum and their combination; Use at least a have formula described in the invention (Ia), (Ib) and (II) in any precursor, the second layer of deposition cupric is to ground floor, so that the substrate of multilayer to be provided, and wherein deposition provides about 20 dusts that are included on the ruthenium zone to about 2, the second layer of first thickness of 000 dust is included in about 0 on the copper zone to about 1 with providing, the second layer of second thickness of 000 dust, wherein first thickness is greater than second thickness, and wherein at least a portion of deposition be have reducing agent in the presence of carry out.

Another aspect, preparation provided herein comprises the technology of substrate of the multilayer of the ground floor and the second layer, this technology comprises: ground floor is provided, it comprises barrier zones and copper zone, and this barrier zones comprises and is selected from least a of titanium, tantalum, tungsten, chromium, molybdenum, zirconium, ruthenium, rhodium, iridium, vanadium, platinum and their combination; Deposit the second layer of cupric to ground floor with at least a copper precursors of use, so that the substrate of multilayer to be provided, wherein deposition provides about 20 dusts that are included on the barrier zones to about 2, the second layer of first thickness of 000 dust is included in about 0 on the copper zone to about 1 with providing, the second layer of second thickness of 000 dust, wherein first thickness is greater than second thickness, and wherein at least a portion of deposition be have reducing agent in the presence of carry out.

The brief description of some accompanying drawing views

Fig. 1 is transmission electron microscope (TEM) photo with ruthenium substrate of Continuous Copper layer, and this copper layer is by using Cu ((CH ₂) ₃NCCHC (NCH ₂CH ₂OSiMe ₂C ₂H ₃) Me) and precursor ALD technology and deposit, described in embodiment 1.

Fig. 2 is the TEM photo that is exposed to ALD circulation and hydrogen annealing circulation copper substrate before, described in embodiment 1.

Fig. 3 is the TEM photo of the copper substrate after the then multiple ALD circulation of hydrogen annealing circulation, and as described in the embodiment 1.

Detailed description of the invention

Technology described in the invention can allow deposition from the copper layer that closes up (self-healing) and self termination, to metallicly stop, on seed and/or the adhesive layer, picture, for example, the zone or the metal level that contain ruthenium, and the copper layer of unlikely formerly deposition or the zone is upper or in some instances, the sedimentation rate that substantially reduces is on the copper zone of deposition formerly. The copper layer of new deposition or additional copper layer are that " certainly closing up " is because it fills the space between the copper zone that formerly deposits, and, if copper coalescent begins to take place, its fill stopping of exposing, seed and/or adhesive layer with the copper film that recovers deposition formerly to continuous state. In addition the copper of new deposition or additional copper layer be " self termination " because in case stop, copper layer that seed and/or adhesive layer are newly deposited covers fully, there is not further copper deposition to take place to the copper layer or zone that formerly deposit, perhaps further deposition reduces significantly, and thereby effective growth of copper stops, thereby caused at least two kinds of thickness in additional copper layer or the second bronze medal layer. Therefore, depend on process conditions, the control sedimentation time can guarantee that also in fact continuous copper layer deposition is at least a portion of ruthenium containing metal layer. What term " in fact continuous copper film " was described is a kind of film, wherein copper be＜200 dusts are thick and form and does not have in fact interruption and continuous copper metal film. In some preferred example, technology described in the invention is used at the complex that is numbered the volatile metal beta-ketimine described in 7034169 and 7205422 the United States Patent (USP), these patents have for the application's surrenderee and with they full content by reference in the present invention with reference. In these examples, volatile metal beta-ketimine and beta-diimine complex provide special advantage for technology described in the invention, contain on ruthenium layer or regional the copper layer or zone upper rather than extremely formerly deposition because copper preferentially is deposited into. In other words, for those be combined with barrier material or the zone the layer for example as ruthenium and copper, the additional copper that uses precursor described in the invention and deposit (for example provides additional copper thickness or additional copper layer at barrier metal or ruthenium, at least 50 nanometers (nm) or still less), thickness does not increase or reduces but on the copper of deposition formerly.

Technology described in the invention is for the preparation of the substrate of multilayer, and it has at least two-layer: ground floor and the second layer. Ground floor has barrier zones or contains the zone of barrier material and the copper zone of deposition formerly, and this barrier material comprises and is selected from least a of titanium, tantalum, tungsten, chromium, molybdenum, zirconium, ruthenium, rhodium, iridium, vanadium, platinum and their combination. The second layer of cupric is with at least two kinds of thickness or with first thickness and second thickness, is deposited on respectively to comprise barrier material for example as ruthenium and copper zone for example on the ground floor as the copper of deposition formerly. In some instances, technology described in the invention allows the additional or second bronze medal layer that deposition has first thickness to the barrier zones of ground floor, wherein first thickness be from about 20 dusts (

) to about 2000 dusts. From about 20 dusts to about 2 according to first thickness of the second layer, disclosure in the scope of 000 dust, the applicant plans to enumerate this thickness can be selected from about 20, about 30, about 40, about 50, about 60, about 70, about 80, about 90, about 100, about 150, about 200, about 250, about 300, about 350, about 400, about 450, about 500, about 550, about 600, about 650, about 700, about 750, about 800, about 850, about 900, about 950, about 1,000, about 1,050, about 1,200, about 1,250, about 1,300, about 1,350, about Isosorbide-5-Nitrae 00, about 1,450, about 1,500, about 1,550, about 1,600, about 1,650, about 1,700, about 1,750, about 1,800, about 1,850, about 1,900, about 1,950, with about 2,000. In addition, the value of first thickness can be any scope of from about 20 to about 2000 (for example, first thickness is from about 50 to about 1 in an example, in 000 the scope), and this any combination that is included in the scope of about 20 dusts between about 2000 dusts (for example, the value of first thickness is from about 100 in about 350 scope, perhaps from about 700 to about 800). Similarly, disclosed other all scopes of the present invention should be explained in the mode that is similar to these two examples. As previously mentioned, by at ALD, CVD, or use is 7 at number in the pulse CV D depositing operation, 205, volatile beta-ketimine described in 422 the United States Patent (USP) or beta-diimine complex, perhaps other use in the prior art or disclose herein contain copper precursors, with suitable reducing agent gas for example as hydrogen or formic acid, be deposited into the second layer of cupric on the barrier layer that contains ruthenium and/or other transition metal with first thickness, wherein process conditions (for example, time, temperature, pressure etc.) be suitable for optionally deposits of fresh copper or the second layer on ruthenium, with than depositing in bigger thickness on the copper zone of deposition formerly or on the copper zone in ground floor.

The second layer that is deposited on the copper zone of ground floor deposits with second thickness, wherein second thickness have from about 0 dust (

) to the scope of about 1,000 dust. In some instances, second thickness can be to be essentially 0, for example, does not have the copper of the additional second layer to be deposited on the copper zone. In other example, the copper of additional thickness is deposited on the copper zone, but with less than its amount on the barrier material zone. In some instances, compared to first thickness, second thickness is to when young about 90%, to when young about 80%, to when young about 70%, to when young about 60%, to when young about 50%, to when young about 40%, to when young about 30%. In the second layer is deposited into example on the copper zone with second thickness, second thickness be from about 0 dust in the scope of about 1,000 dust. The applicant plans to enumerate second thickness can be selected from about 0, about 10, about 20, about 30, about 40, about 50, about 60, about 70, about 80, about 90, about 100, about 150, about 200, about 250, about 300, about 350, about 400, about 450, about 500, about 550, about 600, about 650, about 700, about 750, about 800, about 850, about 900, about 950 and about 1,000. In addition, the value of second thickness can be any scope of from about 0 to about 1000 (for example, in an example second thickness be from about 50 to about 1000 scope), and this is included in about 0 dust to about 1, any combination of the scope between 000 dust (for example, the value of second thickness is from about 100 in about 350 scope, perhaps from about 700 to about 800). Similarly, disclosed other all scopes of the present invention should be explained in the mode that is similar to these two examples.

In some instances, copper film or the second layer of additional thickness are deposited on the barrier layer, and do not have in fact additional thickness or the second layer to be deposited on the copper zone that formerly deposits. In this or other example, the role that the fresh copper that deposits in the process of the deposition cupric second layer can serve as the gap in the copper zone that " filling " formerly deposit is so that in fact continuous copper film to be provided but can not add to copper film the additional thickness of essence. Therefore, in an example, this technology provides additional copper layer or ultra-thin copper film on the ruthenium zone, and the final thickness of film is relating to copper precursors, reducing agent picture whereby, and for example hydrogen or formic acid and barrier layer ruthenium obtains in limited reactions. When not expecting to be subject to theory, it is believed that at ruthenium surface ruthenium and activated hydrogen or formic acid to the reduction of copper precursors, and when copper film begins growth and cover the ruthenium surface, some hydrogen still can diffuse through copper and arrive the ruthenium interface and become activated state in this its and can spread and be back to the copper surface, in this itself and fresh copper precursors react to deposit more copper metal. Copper film reaches the diffusion termination that thickness reaches certain value hydrogen described above so this process continues to carry out, and at this point, does not have additional copper can be deposited on the surface of exposure, and perhaps further the speed of copper deposition reduces significantly.

Except the use that produces thin and continuous copper " seed " layer, technology described in the invention also is very effective for through hole and the groove structure take barrier film such as ruthenium as lining by coming the depth of cracking closure etching with copper CVD or ALD. Like this, the preparation of conductive copper interconnection can directly realize in a step, and can avoid at first preparing the needs of copper seed layer, and this copper seed layer will stand electro-coppering subsequently. The direct filling meeting of small through hole and groove to those＞the wide example of 45 nanometers (nm) has special attraction, because because the copper seed is not conformal, they can be very challenging with conventional P VD copper seed/plating filling. When not expecting to be subject to theory, believe when inside that conformal copper film begins to be deposited on through hole for example or groove when realizing that copper is filled completely, grow to if copper growth preferentially occurs on the barrier liners on the copper of deposition formerly, it can be favourable. Form in infringement in the situation of continuous copper film, this can suppress the generation of the growth of individual copper crystal grain. Therefore, copper film is based upon the inside of through hole or groove in a controlled manner, and avoided the formation in space, this space can betide when big copper crystal grain grows until they are when finally contacting the space that stays between them toward each other from the relative sidewall of through hole or groove. In addition, in case when being completely covered to certain degree of depth owing to ruthenium, the growth rate of copper significantly reduces, the undue growth of the copper on the top of through hole or groove (for example " floating layer (overburden) ") has been avoided, thereby has reduced the amount of the copper for the treatment of that the back is removed by chemically mechanical polishing. Because the deposition that surmounts the maximum film thickness degree has caused not having further copper growth, the self termination growth of this copper film also helps to make the technology controlling and process of final copper film thickness can be better.

As mentioning before, some example of technology described herein uses one or more to have following molecular formula (Ia), (Ib) and copper precursors (II):

In the superincumbent molecular formula, M is the metal that is selected from Cu, Au, Ag, Co, Ru, Rh, Pt, In, Pd, Ni and Os. In some instances, metallic atom M is copper. In molecular formula (Ib), X can be oxygen, thereby forms the ketimide complex, or X can be NR alternatively⁵Thereby form the diimine ligand compound. In above-mentioned molecular formula, substituent R¹、R ²、R ³And R⁵(X is not in the example of O in molecular formula Ib) is selected from hydrogen atom independently of one another; Halogen atom; Has NO₂The nitro of formula; Has formula C_nH _2n+1Alkyl, wherein n is from 1 to 20 numeral; Has formula C_nH _xF _yFluoro-alkyl, wherein the result of (x+y) equals the result of (2n+1), and n is from 1 to 20 numeral; Has formula (R⁶) ₃The alkyl silane of Si, wherein R⁶Be alkyl, alkoxyl or acid amides independently of one another, it comprises 1 to 20 carbon atom; The aromatic group that comprises 6 to 12 carbon atoms; The aromatic group that comprises the alkyl replacement of 6 to 12 carbon atoms; The aromatic radical that comprises the fluoro-alkyl replacement of 6 to 12 carbon atoms; The fluoro aromatic radical that comprises 6 to 12 carbon atoms; Has formula (CH₂) _nO(C _mH _2m+1) ether, wherein n and m are from 1 to 20 numeral independently; Has formula (C_nH _xF _y)O(C _mH _wF _z) fluoro-ether, (x+y)=2n wherein, (w+z)=(2m+1), n and m are from 1 to 20 numeral independently of one another; Has formula (R⁷) ₃The silyl ether of SiO, wherein R⁷The aromatic radical that comprises the alkyl of 1 to 20 carbon atom or comprise 6 to 12 carbon atoms independently of one another; The alkoxyl that comprises 1 to 20 carbon atom; With the acid amides that comprises 1 to 20 carbon atom. In above-mentioned molecular formula, substituent R⁴To be selected to have formula C_nH _2n+1Alkyl, wherein n is from 1 to 20 numeral; Has formula C_nH _xF _yFluoro-alkyl, wherein the result of (x+y) equals the result of (2n+1), and n is from 1 to 20 numeral; Has formula (R⁶) ₃The alkyl silane of Si, wherein R⁶Be alkyl, alkoxyl or acid amides independently of one another, it comprises 1 to 20 carbon atom; The aromatic radical that comprises 6 to 12 carbon atoms; The aromatic radical that comprises 6 to 12 carbon atoms that alkyl replaces; The aromatic radical that comprises 6 to 12 carbon atoms that fluoro-alkyl replaces; The fluoro aromatic radical that comprises 6 to 12 carbon atoms; Has formula (CH₂) _nO(C _mH _2m+1) ether, wherein n and m are from 1 to 20 numeral independently; Has formula (C_nH _xF _y)O(C _mH _wF _z) fluoro-ether, (x+y)=2n wherein, (w+z)=(2m+1), and n and m are from 1 to 20 numeral independently of one another; Has formula (R⁷) ₃The silyl ether of SiO, wherein R⁷The aromatic radical that comprises the alkyl of 1 to 20 carbon atom or comprise 6 to 12 carbon atoms independently of one another; The alkoxyl that comprises 1 to 20 carbon atom; With the acid amides that comprises 1 to 20 carbon atom and R wherein⁴Make hydrogen, atom or group cancellation with the L combination. And in above-mentioned molecular formula, L is ligand, is selected from the alkyl nitrile that comprises 2 to 20 carbon atoms; Has formula (R⁸) ₃The silicyl nitrile of SiCN, wherein R⁸Be alkyl, alkoxyl or acid amides independently of one another, it comprises 1 to 20 carbon atom; The alkynes that comprises 1 to 20 carbon atom; Has formula (R⁹) ₃SiCCR ¹⁰Silicyl alkynes, R wherein⁹Be alkyl, acid amides or alkoxyl independently of one another, it comprises 1 to 20 carbon atom, and R¹⁰Hydrogen, alkoxyl, acid amides or the alkyl that comprises 1 to 20 carbon atom; Has formula (R¹¹) ₃SiCCSi(R ¹¹) ₃Silicyl alkynes, R wherein¹¹Be alkyl, acid amides or alkoxyl independently of one another, it comprises 1 to 20 carbon atom; The alkene, alkadienes or the triolefin alkyl that comprise 1 to 20 carbon atom; Has formula (R¹²) ₃SiCR ¹³C(R ¹³) ₂Silicyl alkene, R wherein¹²Be alkyl, alkoxyl, vinyl, aromatic radical or acid amides independently of one another, it comprises 1 to 20 carbon atom, and R¹³Hydrogen or the alkyl that comprises 1 to 20 carbon atom independently of one another; Has formula (R¹⁴) ₃SiCR ¹³CR ¹³Si(R ¹⁴) ₃Dimethyl silanyl alkene, R wherein¹⁴Be alkyl, alkoxyl or acid amides independently of one another, it comprises 1 to 20 carbon atom, and R¹³Hydrogen atom or the alkyl that comprises 1 to 20 carbon atom independently of one another; The allene derivative that comprises 3 to 20 carbon atoms; Has formula (R¹⁵) ₂CCC(R ¹⁵) ₂The allene derivative, R wherein¹⁵Be hydrogen atom independently of one another or have formula (R¹⁶) ₃The alkyl silane of Si, wherein R¹⁶Be alkyl, acid amides or alkoxyl independently of one another, it comprises 1 to 20 carbon atom; Has formula R¹⁷The alkyl isocyanide of NC, wherein R¹⁷It is the alkyl that comprises 1 to 20 carbon atom; Has formula (R¹⁸) ₃The silicyl isocyanide of SiNC, wherein R¹⁸Be alkyl, acid amides or alkoxyl independently of one another, it comprises 1 to 20 carbon atom; With the aromatic radical that comprises 6 to 12 carbon atoms and wherein L make hydrogen, atom or group cancellation with same R⁴In conjunction with.

The term " alkyl (alkyl) " that the present invention uses comprises the groups of straight chain, side chain or ring-type, comprises 1 to 20 carbon atom or 1 to 10 carbon atom. Typical alkyl group comprises methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, tertiary pentyl, n-pentyl, n-hexyl, cyclopenta and cyclohexyl. Term " alkyl (alkyl) " is also for the moieties that represents to be contained in other groups such as haloalkyl, alkylaryl or the aromatic radical alkyl. The term " aromatic radical " that the present invention uses comprises 6 to 18 yuan the carbocyclic ring with fragrance characters. Typical aromatic radical group comprises phenyl and naphthyl group. Term " aromatic radical that alkyl replaces " is used for the aromatic radical part that expression is replaced by alkyl. The aromatic radical group that typical alkyl replaces comprises tolyl and xylyl group. Term " halogen (halo) " and " halogen (halogen) " comprise fluorine, chlorine, bromine or iodine. Term " fluoro-alkyl " is used for the moieties that one or more its hydrogen atom of expression is substituted by the fluorine halogen atom, can be to be fluorinated partially or entirely, and comprise the alkyl group that comprises 1 to 20 carbon atom or 1 to 10 carbon atom of fluoridizing of straight chain, side chain or ring-type. Typical fluoro-alkyl group comprises-CF₃、-CF ₂CF ₃、-CH ₂CF ₃、-CF ₂CFH ₂, or-CH₂CF ₂CF ₃ In some instances, some in the group that the present invention discusses can be by one or more other elements replace, for example as halogen atom or other hetero atom for example as O, N, Si or S.

In molecular formula (Ia) or (Ib), substituent R⁴To such an extent as to so select and ligand L combination. And, to such an extent as to ligand L so select can and R⁴In conjunction with. Believe ligand L and substituent R⁴All make hydrogen, atom or group cancellation so that L and R⁴Can in conjunction with, thereby cooperate base to be connected with ligand L the ketimide of complex or diimine. In this connection, when L was silicyl alkene, its key can be used for and R⁴In conjunction with. A typical example is Cu (MeC (O) CHC (NCH₂CH ₂OSiMe ₂(C ₂H ₃)) Me). In this example, X is oxygen, and L has formula H₂C＝CHSiMe ₂，R ⁴OCH₂CH ₂，R ³Hydrogen, and R¹And R²It all is Me. In another example, wherein X is NR⁵，R ⁵With L can in conjunction with. In this example, ligand L and substituent R⁵All make hydrogen, atom or group cancellation so that R⁵With L can with the picture R⁴With L in conjunction with such the same mode combination.

In some instances, substituent R⁴Also can be connected to substituent R¹、R ²And/or R³ In these examples, work as R¹、R ²And/or R³Neither hydrogen atom, halogen atom neither the NO of nitro group₂The time, substituent R⁴Can be only and substituent R¹、R ²And/or R³Connect.

In some example of complex described in the invention, X is NR ⁵, and R ⁵Can be above-mentioned as R ¹, R ²Or R ³Any group or atom.In these examples, ligand (L), or additional alternatively ligand (L), it can be above-mentioned any group or atom, also can be connected to substituent R ⁵Also has substituent R ⁴In these examples, believe that at least one ligand L has, for example, available coordination valence, by its with and R ⁵Thereby cooperate base to be connected with ligand L in conjunction with diimine with complex.In this or other example, substituent R ⁵Also can be connected to substituent R ¹, R ², R ³, and/or R ⁴Whole or any one is to form circulus.In the example of back, substituent R ⁵With substituent R ¹, R ²And/or R ³Connect, only work as R ¹, R ²And/or R ³Neither hydrogen atom, halogen atom, neither the NO of nitro group ₂The time, perhaps work as R alternatively ⁵When being hydrogen atom.

In some instances, substituent R ⁴, and/or if X is NR ⁵Substituent R alternatively ⁵To such an extent as to, can be adjusted ligand L coordination to the metal center of adjacent complex rather than the metal center of himself.In these examples, other complex for example as, but (triametric) and four poly-(tetrametric) complexs of being not limited to (diametric), the trimerization of dimerization can form.

In some instances, substituent R ¹, R ², and R ³Whole or any one can be connected independently to form circulus.In some instances, R ¹And R ²And/or R ²And R ³Can be connected independently to form circulus.

In some instances, copper precursors described in the invention can contain fluorine.In these examples, substituent R ¹, R ², R ³, R ⁴Or R ⁵Whole or any one can contain fluorine, as, for example, the aromatic radical that fluoro-alkyl, fluoro-alkyl replace, fluoro aromatic radical, the fluoro aromatic radical that alkyl replaces, or the fluoro aromatic radical group that replaces of fluoro-alkyl.In example alternatively, copper precursors described in the invention does not contain fluorine.The example of fluorine-containing copper precursors includes but not limited to:

Cu(CF ₃C(O)CHC(NCH ₂CH ₂OSiMe ₂C ₂H ₃)CF ₃)，

Cu(CF ₃C(O)CHC(NCH ₂CH ₂OSiMe ₂C ₂H ₃)Me)，

Cu(CF ₃C(O)CHC(NCH ₂CH ₂NMeSiMe ₂C ₂H ₃)CF ₃)，

Cu(CF ₃C(O)CHC(NCH ₂CH ₂NMeSiMe ₂C ₂H ₃)Me)，

Cu (CF ₃C (O) CHC (NCH ₂CHMeOSiMe ₂C ₂H ₃) CF ₃) and

Cu(CF ₃C(O)CHC(NCH ₂CHMeOSiMe ₂C ₂H ₃)Me)。

In some instances, metal complex has molecular formula (II).In these examples, ligand L for example can be, alkynes or diene, and coordination to two a metallic ketimide unit are showed in molecular formula (II) as following.In these examples, metallic atom M can be identical, perhaps is different metallic atoms alternatively.In the latter's example, this can allow to deposit the hybrid metal film.

In an example, the ligand L in any above-mentioned molecular formula can be an alkyl nitrile, for example as but be not limited to CH ₂CN or Me ₂CH ₂CCN.For L, in this and aforesaid example, for the group of ligand L regulation can make the hydrogen atom cancellation with allow can and R ⁴Connect.In an optional example, ligand L can be the silicyl nitrile, for example as but be not limited to Me ₂CH ₂SiCN.In further example, ligand L can be an alkynes, for example as but be not limited to CH ₂CCMe or CH ₂CCH.In another example, ligand L can be an alkene, for example as but be not limited to Me ₃CCHCH ₂Or Me (CH ₂) ₂CHCH ₂In example further, ligand L can be the allene derivative, for example as but do not limit CHCCCH ₂Or MeCCCMe ₂In an example, ligand L can be an alkyl nitrile, for example as but be not limited to MeCN or Me ₃CCN.In further example, ligand L can be an alkynes, for example as but be not limited to MeCCMe or MeCCH.In another example still, ligand L has formula (R ¹⁰) ₃SiCR ¹⁷C (R ¹⁷) ₂Silicyl alkene, or have formula (R ¹¹) ₃SiCR ¹⁷CR ¹⁷Si (R ¹¹) ₃Dimethyl silanyl alkene, for example as but be not limited to Me ₃SiCHCH ₂, Me ₃SiCHCHSiMe ₃, (MeO) ₃SiCHCH ₂, or (EtO) ₃SiCHCH ₂In another example, ligand L can be an alkyl isocyanide, for example as but be not limited to Me ₃CNC.In further example, ligand L has formula (R ¹⁵) ₃SiC (R ¹⁷) ₂CR ¹⁷C (R ¹⁷) ₂Allyl silicane, for example as but be not limited to (MeO) ₃SiCH ₂CHCH ₂, (i-Pr) ₃SiCH ₂CHCH ₂And Me ₃SiCH ₂CHCH ₂In aforesaid formula and run through in the specification, term " Me " expression methyl, " Et " expression ethyl and " i-Pr " expression isopropyl.

In above-mentioned molecular formula (I), the organic metal key between metal or copper atom and ligand (L) is 2 singly-bounds or 1 singly-bound.In some instances, copper atom to L, copper atom to O and/or copper atom bond energy between at least one its to the N can be weaker than the bond energy of setting up in the balance at complex.Believing like this can be in some cases and under some process conditions, allows complex to be decomposed into its part easily at these special key places.

In other example, copper precursors can be any of employed copper precursors in the prior art of copper layer deposition, particularly CVD or ALD deposition.Two kinds of kind commonly used that have been used to the copper Organometallic precursor of CVD, ALD or other depositions are Cu (I) and Cu (II) precursor.A kind of Cu (I) precursor commonly used is the precursor with molecular formula " Cu (I) is (W) (hfac) ", and wherein " hfac " represents 1,1,1,5,5,5-hexafluoro-2,4-pentanedione anion and (W) represent the ligand picture of indifferent equilibriumization, for example alkene, alkynes or trialkyl phosphine.A specific example with Cu (I) precursor of aforementioned molecular formula is 1,1,1,5,5,5-hexafluoro-2,4-pentanedione-copper (I) trimethyl-ethylene base silane (below be written as Cu (hfac) (tmvs)), (the application's PA) assignee is with trade mark CUPRASELECT for Air products Chemical, Inc.ofAllentown by the air products of Pennsylvanian Allentown and chemical Co., Ltd for it ^TMAnd sell.And the type of another kind of Cu (I) precursor is the precursor with molecular formula " (X) Cu (Y) ".In these special Cu (I) precursors, " X " is organic anion, and " Y " be the ligand of indifferent equilibriumization, as, trialkyl phosphine for example.An example of this precursor is CpCuPEt ₃, wherein Cp is a cyclopentadienyl group, and PEt ₃It is triethyl phosphine.An example that can be used in Cu (II) precursor of technology described in the invention has chemical formula Cu (II) (Z) ₂, wherein (Z) is organic anion.The example of such precursor includes but not limited to Cu (II) two (beta-diketon), Cu (II) two (beta-diimine) and Cu (II) two (beta-ketimine) complex.The further example of other copper precursors includes but not limited to copper formate and Cu (II) ethyl acetoacetate.

As previously mentioned, copper precursors described in the invention can be as the precursor of the film of deposited copper, cupric or its alloy in substrate.The example of suitable substrate includes but not limited to, semi-conducting material for example as GaAs (" GaAs "), boron nitride (" BN ") silicon and the synthetic that contains silicon for example as crystalline silicon, polysilicon, amorphous silicon, epitaxial silicon, silicon dioxide (" SiO ₂"), carborundum (" SiC "), silicon oxide carbide (" SiOC "), silicon nitride (" SiN "), carbonitride of silicium (" SiCN "), silicone glass (" OSG "), organic fluorinated silicone silicate glass (" OFSG "), fluorosilicate glass (" FSG ") and other suitable substrates or their mixture.Matrix can further comprise multiple layer, and film will be applied thereto, for example resemble antireflection layer, photoresist, organic polymer, porous is organic and inorganic material, metal for example as copper and aluminium or diffusion impervious layer.Copper precursors can use described in the invention or any deposition techniques well known in the prior art.The typical sedimentary technology includes but not limited to chemical vapor deposition (CVD), ald (ALD), pulse CV D, plasma auxiliary chemical vapor deposition (PACVD) and plasma enhanced chemical vapor deposition (PECVD).

In some instances, use CVD or ALD technology that copper precursors is deposited in the substrate.In some instances, the deposition of copper precursors can be carried out under 400 ℃ or lower temperature, perhaps 200 ℃ or lower or 100 ℃ or lower.In typical C VD depositing operation, copper precursors is introduced into into reative cell for example as in the vacuum chamber.In some instances, except copper precursors, other chemical reactor can before the introducing of copper precursors, during and/or be introduced into afterwards.Energy source, as, for example heat, plasma or other sources, thus excited copper precursors and optionally chemical reactor at least a portion of substrate, formed film.

Served as barrier layer, Seed Layer and/or adhesive layer contain the ruthenium layer can use one or more Organometallic precursor for example as but be not limited to di-(cyclopentadienyl)ruthenium, three (2,2,6,6-tetramethyl-3,5-heptadione) ruthenium, acetylacetone,2,4-pentanedione ruthenium and ruthenium deposit.The deposition that contains the ruthenium layer can use any technology described in the invention or other method well known in the prior art to carry out.

As previously mentioned, in some instances, chemical reactor can be before the introducing of copper precursors, during and/or be introduced in the reative cell afterwards.The selection of chemical reactor can depend on the composition of expected result film.For example, in an example and the reaction of halogen-containing chemical reactor may form the metal halide film, and in another example and the reaction of oxidant chemical reactor will produce metal oxide film.Typical chemical reactor includes, but are not limited to oxidant (O for example ₂, NO, NO ₂, O ₃, CO, CO ₂Deng); Water; Halide; Halogen-containing silane; Alkylchlorosilane, alkyl bromide silane, or alkyl iodide silane; The silicon halide complex is for example as silicon tetrachloride, silicon bromide or silicon tetraiodide; The tin complex of halo is for example as the tetraalkyl stannane, alkyl chloride stannane, alkyl bromide stannane, or alkyl iodide stannane; The germane complex is for example as the alkyl chloride germane, alkyl bromide germane, or alkyl iodide germane; The boron trihalides complex is for example as boron chloride, Boron tribromide, or triiodide boron; The aluminum halide complex is for example as aluminium chloride, aluminium bromide or silver iodide; The halide of alkyl aluminum; The gallium halide complex is for example as gallium trichloride, tribromide gallium, or triiodide gallium; Perhaps their combination.The derivative that also can predict above-mentioned complex also can use.Chemical reactor can be used as gas and directly is transported to reative cell, is transferred and/or is transported in the reative cell by inert carrier gas as the liquid of vaporization, the solid of distillation.The example of inert carrier gas comprises nitrogen, hydrogen, argon, xenon etc.

In another example, comprise in the metal described in the invention any film can have reducing agent in the presence of be deposited on the surface of substrate, for example film is reduced to the metal of expection.In an example, the copper precursors with molecular formula (I) can be introduced in CVD or the ALD reactor together with reducing agent.Reducing agent is typically introduced with gas form.The example of suitable reducing agent comprises, but (for example be not limited to alcohol, carboxylic acid, hydrogen, hydrogen plasma, long-range hydrogen plasma (remote hydrogen plasma), silane, diethylsilane, ethylsilane, dimethylsilane, phenyl silane, silane, disilane, amino silane), borine (for example, borine, diborane), aluminium alkane, germane, hydrazine, ammonia or their mixture.In a special example, reducing agent is a formic acid.

In some instances, copper film is to be deposited by the ALD depositing operation by the copper precursors with molecular formula (I).In typical A LD technology, precursor one or more gases or that vaporized is introduced in the process chamber of having accommodated substrate with the pulse that replaces in a process cycles.Preferably, each process cycles forms only about one deck monolayer of material, by adsorbing and preferably passing through chemisorbed.The number of times of process cycles of rete of being used to grow depends on desired thickness but generally can surpass 1000 or more periods.For semiconductor device, repetition process cycles up in double damask structure stop or Seed Layer has enough thickness to carry out the function of its expection.

In ALD technology, substrate is remained on the temperature range that is beneficial to chemisorbed, for example, enough low with complete key between the material that remains on absorption and the following substrate, and enough height with the condensation of avoiding precursor with in each process cycles, to provide enough activation energy for required surface reaction.The temperature of process chamber can be in 0 ℃ to 400 ℃ scope, or from 0 ℃ to 300 ℃, or from 0 ℃ to 275 ℃.During ALD technology, the pressure in the process chamber can be in the scope of from 0.1 to 1000 holder, or from 0.1 to 15 holder, or 0.1 to 10 holder.Yet what will understand is that for any specific ALD technology, temperature and pressure may depend on one or more precursors that comprised and change.

Any aforesaid film formation method described in the invention, and other film formation method well known in the prior art can separately or be united use.Other the deposition process that can use comprises, for example, ionized metal plasma (IMP), physical vapor deposition (PVD), chemical vapor deposition (CVD), ald (ALD), plasma auxiliary chemical vapor deposition (PACVD), plasma enhanced chemical vapor deposition (PECVD) is electroplated, and electroless plating.For example, in an example, the copper-containing film of mix forming can be by the oxidation film of deposited copper in turn, succeeded by the copper metal film, and then reduces this multilayer film and form so that the fine copper film to be provided.

In some instances, copper precursors described in the invention for example can be dissolved in the The suitable solvent as amine (for example, triethylamine), ether (for example, THF), the solvent that discloses of aromatic compound (for example, toluene) or any other the present invention, to form solution.The solution of gained can be used for steam and be delivered to ALD or CVD reative cell directly being flashed in liquid injection (DLI) system.In other example, before being incorporated into the DLI system, complex described herein can be dissolved in stabilisation liquid for example as in alkene or the alkynes.

Embodiment

Embodiment 1:Cu ((CH ₂) ₃NCCHC (NCH ₂CH ₂OSiMe ₂C ₂H ₃) Me) precursor is at ruthenium but not the suprabasil selective deposition of copper.

The silicon wafer that will have the thick copper film of approximate 200 dusts (its deposit by physical vapour deposition (PVD) and have 99.999% purity) is cut into 3 sample aliquot sheets, called after C1, C2 and C3.Copper precursors Cu ((CH with 2.0 grams ₂) ₃NCCHC (NCH ₂CH ₂OSiMe ₂C ₂H ₃) Me) sample packs in the source container of the reactor that is suitable for ALD technology of laboratory size, and be sealed in the nitrogen.The temperature of container then is adjusted to 90 ℃.With ruthenium substrate sample, R1 and copper sample C1 pack in the process chamber of ALD reactor and pure hydrogen under the pressure of 0.5 holder with the continuous flow of 20 squares of cubic centimetre per minutes (sccm) by above them.The temperature of substrate is adjusted to 375 ℃, thereby and any primary Cu oxide that under the continuous flow of pure hydrogen, keeps being present in the copper substrate surface in a hour be reduced to metallic copper.

In other experiment, identical copper sample C2 is heated 1 hour to produce the Cu oxide layer of the visible purple of vision in 175 ℃ in air atmosphere.This copper sample C2 is heated to 375 ℃ and lasting one hour in the hydrogen of 20sccm, and its color restoration has arrived metallic copper.This proof is effective to the reducing process of copper substrate.

In other experiment, copper sample C3 carries out the cross section imaging by transmission electron microscope (TEM).

In the ALD reactor, heating copper and ruthenium sample C1 and R1 were cooled to 150 ℃ with samples after one hour in hydrogen stream in 375 ℃ of hydrogen at 20sccm.The ALD reactor sequences then is activated, wherein each circulation, and copper precursors, nitrogen, hydrogen, nitrogen and copper precursors are corresponding to independently of one another pulse 15,5,60,5 and 15 seconds, continue 2372 circulations altogether.Reactor then is cooled, and substrate is moved out of and is used for the TEM imaging.

The result of the TEM of ruthenium substrate R1 clearly illustrates and deposited the thick copper of 2000 dusts, as shown in Fig. 1 of the enlargement ratio reference bar that has 100nm.Secondly, do not have additional copper to be deposited on the copper sample C1 in fact, this is by relatively its TEM image (Fig. 2) and (Fig. 3) of copper sample C3 determine.Fig. 2 and 3 has shown that copper substrate C1 has identical in fact thickness with C3, seems coarse slightly than C3 though notice the surface of C1, this be before experience due to 375 ℃ of thermal annealings that continue 1 hour.Therefore, it be it seems has proved that copper is optionally to deposit to ruthenium but not on the copper.

Embodiment 2:Cu (CF ₃C (O) CHC (NCH ₂CH ₂OSiMe ₂C ₂H ₃) CF ₃) precursor is at ruthenium but not the suprabasil selective deposition of copper.

With copper precursors Cu (CF ₃C (O) CHC (NCH ₂CH ₂OSiMe ₂C ₂H ₃) CF ₃) in as described in Example 1 the identical ALD reactor of packing into, pack into together with four different ruthenium substrates and the substrate of a PVD copper.Except that using identical in hydrogen 375 ℃ of preheatings and then starting 670 ALD circulations, use as moving this system top same circulation timei for precursor, nitrogen and hydrogen succeeded by being cooled to 150 ℃.On PVD copper, do not observe the deposition of copper, but seen that by TEM the copper of 200 dusts is deposited on the ruthenium sample.

In the result of two kinds of different precursors described in using embodiment 1 and 2, ALD copper all optionally grows on the ruthenium, rather than in the substrate of PVD copper, and pass through auger spectrum and determine.

Claims

1, a kind of method that is used to prepare the substrate of the multilayer that comprises the ground floor and the second layer, this method comprises:

The ground floor that comprises ruthenium zone and copper zone is provided;

Use at least a have following molecular formula (I a), (I b) and (II) in any precursor deposit cupric the second layer to ground floor, so that the substrate of multilayer to be provided:

Wherein M is a copper;

Wherein X is selected from oxygen and NR ⁵

R wherein ¹, R ², R ³And R ⁵Be selected from hydrogen atom independently of one another; Halogen atom; Has formula NO ₂Nitro; Has formula C _nH _2n+1Alkyl, wherein n is from 1 to 20 numeral; Has formula C _nH _xF _yFluoro-alkyl, wherein the result of (x+y) equals the result of (2n+1), and n is from 1 to 20 numeral; Has formula (R ⁶) ₃The alkyl silane of Si, wherein R ⁶Be alkyl, alkoxyl or acid amides independently of one another, it comprises 1 to 20 carbon atom; The aromatic radical that comprises 6 to 12 carbon atoms; The aromatic radical that comprises 6 to 12 carbon atoms that alkyl replaces; The aromatic radical that comprises 6 to 12 carbon atoms that fluoro-alkyl replaces; The fluoro aromatic radical that comprises 6 to 12 carbon atoms; Has formula (CH ₂) _nO (C _mH _2m+1) ether, wherein n and m are from 1 to 20 numeral independently; Has formula (C _nH _xF _y) O (C _mH _wF _z) fluoro-ether, (x+y)=2n wherein, (w+z)=(2m+1), and n and m are from 1 to 20 numeral independently of one another; Has formula (R ⁷) ₃The silyl ether of SiO, wherein R ⁷Be the aromatic radical that comprises the alkyl of 1 to 20 carbon atom or comprise 6 to 12 carbon atoms independently of one another; The alkoxyl that comprises 1 to 20 carbon atom; With the acid amides that comprises 1 to 20 carbon atom;

R wherein ⁴Be to be selected to have formula C _nH _2n+1Alkyl, wherein n is from 1 to 20 numeral; Has formula C _nH _xF _yFluoro-alkyl, wherein the result of (x+y) equals the result of (2n+1), and n is from 1 to 20 numeral; Has formula (R ⁶) ₃The alkyl silane of Si, wherein R ⁶Be alkyl, alkoxyl or acid amides independently of one another, it comprises 1 to 20 carbon atom; The aromatic radical that comprises 6 to 12 carbon atoms; The aromatic radical that comprises 6 to 12 carbon atoms that alkyl replaces; The aromatic radical that comprises 6 to 12 carbon atoms that fluoro-alkyl replaces; The fluoro aromatic radical that comprises 6 to 12 carbon atoms; Has formula (CH ₂) _nO (C _mH _2m+1) ether, wherein n and m are from 1 to 20 numeral independently; Has formula (C _nH _xF _y) O (C _mH _wF _z) fluoro-ether, (x+y)=2n wherein, (w+z)=(2m+1), and n and m are from 1 to 20 numeral independently of one another; Has formula (R ⁷) ₃The silyl ether of SiO, wherein R ⁷Be the aromatic radical that comprises the alkyl of 1 to 20 carbon atom or comprise 6 to 12 carbon atoms independently of one another; The alkoxyl that comprises 1 to 20 carbon atom; With the acid amides that comprises 1 to 20 carbon atom, and R wherein ⁴Combine with L by the cancellation that allows hydrogen, atom or group;

Wherein L is a ligand, is selected from the alkyl nitrile that comprises 2 to 20 carbon atoms; Has formula (R ⁸) ₃The silicyl nitrile of SiCN, wherein R ⁸Be alkyl, alkoxyl or acid amides independently of one another, it comprises 1 to 20 carbon atom; The alkynes that comprises 1 to 20 carbon atom; Has formula (R ⁹) ₃SiCCR ¹⁰Silicyl alkynes, wherein R ⁹Be alkyl, acid amides or alkoxyl independently of one another, it comprises 1 to 20 carbon atom, and R ¹⁰Be hydrogen, alkoxyl, acid amides or the alkyl that comprises 1 to 20 carbon atom; Has formula (R ¹¹) ₃SiCCSi (R ¹¹) ₃Silicyl alkynes, R wherein ¹¹Be alkyl, acid amides or alkoxyl independently of one another, it comprises 1 to 20 carbon atom; The alkene, alkadienes or the alkatrienes that comprise 1 to 20 carbon atom; Has formula (R ¹²) ₃SiCR ¹³C (R ¹³) ₂Silicyl alkene, R wherein ¹²Be alkyl, alkoxyl, aromatic radical, vinyl or acid amides independently of one another, it comprises 1 to 20 carbon atom, and R ¹³Be hydrogen independently of one another, comprise the alkyl of 1 to 20 carbon atom or comprise the aromatic radical of 6 to 12 carbon atoms; Has formula (R ¹⁴) ₃SiCR ¹³CR ¹³Si (R ¹⁴) ₃Dimethyl silanyl alkene, R wherein ¹⁴Be alkyl, alkoxyl or acid amides independently of one another, it comprises 1 to 20 carbon atom, R ¹³Be hydrogen atom or the alkyl that comprises 1 to 20 carbon atom independently of one another; The allene derivative that comprises 3 to 20 carbon atoms; Has formula (R ¹⁵) ₂CCC (R ¹⁵) ₂The allene derivative, R wherein ¹⁵Be hydrogen atom independently of one another or have formula (R ¹⁶) ₃The alkyl silane of Si, wherein R ¹⁶Be alkyl, acid amides or alkoxyl independently of one another, it comprises 1 to 20 carbon atom; Has formula R ¹⁷The alkyl isocyanide of NC, wherein R ¹⁷It is the alkyl that comprises 1 to 20 carbon atom; Has formula (R ¹⁸) ₃The silicyl isocyanide of SiNC, wherein R ¹⁸Be the alkyl that comprises 1 to 20 carbon atom independently of one another; With the aromatic group that comprises 6 to 12 carbon atoms, and wherein L by making hydrogen, atom or group cancellation and R ⁴In conjunction with;

Wherein deposition provides the second layer, and this second layer comprises;

About 20 dusts of nail on the zone to first thickness of about 2000 dusts and

On the copper zone about 0 to second thickness of about 1000 dusts and

Wherein first thickness is greater than second thickness.

2, the process of claim 1 wherein X, R ¹, R ², R ³And R ⁴In any be connected to form circulus.

3, the process of claim 1 wherein to have molecular formula by at least one precursor (I a).

4, the process of claim 1 wherein that at least one precursor has molecular formula (I b).

5, the process of claim 1 wherein that at least one precursor has molecular formula (II).

6, the process of claim 1 wherein X and R ¹Be connected to form circulus.

7, the process of claim 1 wherein at least a portion of deposition step be have reducing agent in the presence of carry out.

8, the process of claim 1 wherein that reducing agent is to be selected from least a in alcohol, carboxylic acid, hydrogen, hydrogen plasma, long-range hydrogen plasma, silane, borine, aluminium alkane, germane, hydrazine, ammonia and their mixture.

9, be used to prepare the method for the substrate of the multilayer that comprises the ground floor and the second layer, this method comprises:

The ground floor that comprises barrier zones and copper zone is provided, and this barrier zones comprises and is selected from least a in titanium, tantalum, tungsten, chromium, molybdenum, zirconium, ruthenium, rhodium, iridium, vanadium, platinum and their combination;

Wherein M is a copper;

Wherein X is selected from oxygen and NR ⁵

R wherein ⁴Be to be selected to have formula C _nH _2n+1Alkyl, wherein n is from 1 to 20 numeral; Has formula C _nH _xF _yFluoro-alkyl, wherein the result of (x+y) equals the result of (2n+1), and n is from 1 to 20 numeral; Has formula (R ⁶) ₃The alkyl silane of Si, wherein R ⁶Be alkyl, alkoxyl or acid amides independently of one another, it comprises 1 to 20 carbon atom; The aromatic radical that comprises 6 to 12 carbon atoms; The aromatic radical that comprises 6 to 12 carbon atoms that alkyl replaces; The aromatic radical that comprises 6 to 12 carbon atoms that fluoro-alkyl replaces; The fluoro aromatic radical that comprises 6 to 12 carbon atoms; Has formula (CH ₂) _nO (C _mH _2m+1) ether, wherein n and m are from 1 to 20 numeral independently; Has formula (C _nH _xF _y) O (C _mH _wF _z) fluoro-ether, (x+y)=2n wherein, (w+z)=(2m+1), and n and m are from 1 to 20 numeral independently of one another; Has formula (R ⁷) ₃The silyl ether of SiO, wherein R ⁷Be the aromatic group that comprises the groups of 1 to 20 carbon atom or comprise 6 to 12 carbon atoms independently of one another; The alkoxyl that comprises 1 to 20 carbon atom; With the acid amides that comprises 1 to 20 carbon atom, and R wherein ⁴By hydrogen, atom or group cancellation are combined with L;

Wherein L is selected from the alkyl nitrile ligand that comprises 2 to 20 carbon atoms; Has formula (R ⁸) ₃The silicyl nitrile of SiCN, wherein R ⁸Be alkyl, alkoxyl or acid amides independently of one another, it comprises 1 to 20 carbon atom; The alkynes that comprises 1 to 20 carbon atom; Has formula (R ⁹) ₃SiCCR ¹⁰Silicyl alkynes, wherein R ⁹Be alkyl, acid amides or alkoxyl independently of one another, it comprises 1 to 20 carbon atom, and R ¹⁰Be hydrogen, alkoxyl, acid amides or the alkyl that comprises 1 to 20 carbon atom; Has formula (R ¹¹) ₃SiCCSi (R ¹¹) ₃Silicyl alkynes, R wherein ¹¹Be alkyl, acid amides or alkoxyl independently of one another, it comprises 1 to 20 carbon atom; The alkene, alkadienes or the alkatrienes that comprise 1 to 20 carbon atom; Has formula (R ¹²) ₃SiCR ¹³C (R ¹³) ₂Silicyl alkene, R wherein ¹²Be alkyl, alkoxyl, aromatic radical, vinyl or acid amides independently of one another, it comprises 1 to 20 carbon atom, and R ¹³Be hydrogen independently of one another, comprise the alkyl of 1 to 20 carbon atom or comprise the aromatic radical of 6 to 12 carbon atoms; Has formula (R ¹⁴) ₃SiCR ¹³CR ¹³Si (R ¹⁴) ₃Dimethyl silanyl alkene, R wherein ¹⁴Be alkyl, alkoxyl or acid amides independently of one another, it comprises 1 to 20 carbon atom, and R ¹³Be hydrogen atom or the alkyl that comprises 1 to 20 carbon atom independently of one another; The allene derivative that comprises 3 to 20 carbon atoms; Has formula (R ¹⁵) ₂CCC (R ¹⁵) ₂The allene derivative, R wherein ¹⁵Be hydrogen atom independently of one another or have formula (R ¹⁶) ₃The alkyl silane of Si, wherein R ¹⁶Be alkyl, acid amides or alkoxyl independently of one another, it comprises 1 to 20 carbon atom; Has formula R ¹⁷The alkyl isocyanide of NC, wherein R ¹⁷It is the alkyl that comprises 1 to 20 carbon atom; Has formula (R ¹⁸) ₃The silicyl isocyanide of SiNC, wherein R ¹⁸Be the groups that comprises 1 to 20 carbon atom independently of one another; With the aromatic radical that comprises 6 to 12 carbon atoms, and wherein L by making hydrogen, atom or group cancellation and R ⁴In conjunction with;

Wherein deposition provides the second layer, and this second layer comprises:

About 20 dusts on barrier zones to first thickness of about 2,000 dusts and

On the copper zone about 0 to second thickness of about 1,000 dust, wherein first thickness is greater than second thickness, and wherein at least a portion of deposition be have reducing agent in the presence of carry out.

10, the method for claim 9, wherein reducing agent is to be selected from least a in alcohol, carboxylic acid, formic acid, hydrogen, hydrogen plasma, long-range hydrogen plasma, silane, borine, aluminium alkane, germane, hydrazine, ammonia and their mixture.

11, the method for claim 10, wherein reducing agent comprises hydrogen.

12, the method for claim 10, wherein reducing agent comprises formic acid.

13, the method for claim 9, wherein barrier zones comprises ruthenium.

14, the method for claim 9, wherein at least one precursor has molecular formula (I a).

15, the method for claim 9, wherein at least one precursor has molecular formula (I b).

16, the method for claim 9, wherein at least one precursor has molecular formula (II).

17, the method for claim 9, wherein X and R ¹Be connected to form circulus.

18, be used to prepare the method for the substrate of the multilayer that comprises the ground floor and the second layer, this method comprises:

With the second layer that uses at least a copper precursors to deposit cupric to ground floor, so that the substrate of multilayer to be provided, wherein deposition provides the second layer, this second layer comprises:

About 20 dusts on barrier zones to first thickness of about 2,000 dusts and