CN109950197A - Semiconductor structure and forming method thereof - Google Patents

Abstract

A kind of semiconductor structure and forming method thereof, wherein method includes: offer substrate, has dielectric layer in the substrate, has opening in the dielectric layer；The first adhesion layer is formed in the side wall and bottom surface of the opening, first adhesion layer includes opposite the first face and the second face, and first face is contacted with dielectric layer, and the material on second face surface contains the first bonded atom；Barrier structure is formed on the first adhesion layer the first face surface, the barrier structure includes third face, and the third face and the second face paste are closed, and the material on third face surface contains the first bonded atom, also contains ruthenium atom in the barrier structure；It is formed after the barrier structure, forms interconnection structure in the opening.The better performances for the semiconductor structure that the method is formed.

Description

Semiconductor structure and forming method thereof

Technical field

The present invention relates to field of semiconductor manufacture more particularly to a kind of semiconductor structure and forming method thereof.

Background technique

With the development of semiconductor technology, the integrated level of VLSI chip has been up to several hundred million or even tens The scale of hundred million devices, two layers or more of multiple layer metal interconnection technique are widely used.Traditional metal interconnection is by aluminium At, but with the continuous reduction of device feature size in IC chip, the current densities in metal interconnecting wires constantly increase Add, it is desirable that response time constantly reduce, traditional aluminum interconnecting is no longer satisfied requirement, and it is mutual that copper interconnecting line gradually replaces aluminium Line.Compared with aluminium, copper has lower resistivity and higher electromigration resistance properties, can reduce the resistance capacitance of interconnection line (RC) postpone, improve electromigration, improve device stability.

But copper interconnecting line is also defective.Metallic copper has high mobility, and copper is in silicon and its oxide and most of Jie It is spread in matter very fast.And copper once enters in semiconductor substrate or dielectric layer, will affect device minority carrier lifetime and Leakage current increases the electromigration of interconnection structure, causes circuit malfunction, and reliability reduces.A kind of solution is: being formed, copper is mutual Before line, barrier layer is formed on the substrate, it being capable of a degree of diffusion for stopping copper.

However, the performance for the semiconductor devices that the prior art is formed is still poor.

Summary of the invention

The technical problem to be solved by the present invention is to provide a kind of semiconductor structures and forming method thereof, to improve semiconductor devices Performance.

In order to solve the above technical problems, the embodiment of the present invention provides a kind of forming method of semiconductor structure, comprising: provide Substrate has dielectric layer in the substrate, has opening in the dielectric layer；It is formed in the side wall and bottom surface of the opening First adhesion layer, first adhesion layer include opposite the first face and the second face, and first face and dielectric layer contact, described The material in the second face surface contains the first bonded atom；Barrier structure, institute are formed on the second face surface of first adhesion layer Stating barrier structure includes third face, and the third face and the second face paste are closed, and the first bonded atom is contained in the third face, described Also contain ruthenium atom in barrier structure；It is formed after the barrier structure, forms interconnection structure in the opening.

Optionally, the material of first adhesion layer includes: tantalum nitride, and first bonded atom is nitrogen-atoms.

Optionally, the barrier structure includes the first barrier layer and the second barrier layer on the first barrier layer, described The third face of barrier structure is the binding face on the first barrier layer and the second face.

Optionally, the material on first barrier layer includes: nitridation ruthenium, and the material on second barrier layer includes ruthenium.

Optionally, it is formed after first adhesion layer, is formed before barrier structure, the forming method further include: The second adhesion layer is formed on first adhesion layer；The material of second adhesion layer includes: TaRuN；Second adhesion layer Including opposite fourth face and the 5th face, the 5th face and third face paste are closed, the fourth face and the conjunction of the second face paste, and described the The material on four sides and the 5th face surface also contains the first bonded atom, and the fourth face and the material on the second face surface also contain Second bonded atom, second bonded atom are tantalum atom, and the material on the 5th face and third face surface also contains described Ruthenium atom.

Optionally, the formation process of first adhesion layer includes the first atom layer deposition process, first atomic layer The step of depositing operation includes the first adhesion material film that multiple-layer overlapped is formed using multiple first atomic layer deposition step, every time First atomic layer deposition step forms one layer of first adhesion material film；The parameter of first atom layer deposition process includes: temperature Degree is 200 degrees Celsius~350 degrees Celsius, and pressure is 2 supports~5 supports, the number of the first atomic layer deposition step are as follows: 20 times~40 It is secondary；First atomic layer deposition step includes: that tantalum presoma, part tantalum forerunner are passed through into the opening using the first aeration process Body is adsorbed in side wall and the bottom of opening, forms the first precursor film；It is formed after first precursor film, is taken out using first Gas technique removes the unadsorbed tantalum presoma in opening sidewalls and bottom surface；After first air aspiration process, using second Aeration process is passed through nitrogen presoma into the opening, and part nitrogen presoma reacts to form the first adherency material with the first precursor film Expect film；It is formed after the first adhesion material film, the nitrogen forerunner not reacted with the first precursor film is removed using the second air aspiration process Body.

Optionally, it includes PDMAT that the parameter of first aeration process, which includes: tantalum presoma, and the flow of tantalum presoma is 500 standard milliliters/minute~2000 standard milliliters/minute, the first duration of ventilation are 200 milliseconds~800 milliseconds；Described first takes out The parameter of gas technique includes: that carrier gas includes argon gas, and the first pumpdown time is 1000 milliseconds~3000 milliseconds, and the flow of carrier gas is 2000 standard milliliters/minute~4000 standard milliliters/minute；The parameter of second aeration process includes: that nitrogen presoma includes ammonia Or nitrogen, the flow of nitrogen presoma are 300 standard milliliters/minute~800 standard milliliters/minute, the second duration of ventilation is 500 Millisecond~1500 milliseconds；It includes argon gas that the parameter of second air aspiration process, which includes: carrier gas, and the time of the second pumping is 1000 milliseconds~ 3000 milliseconds, the flow of carrier gas is 2000 standard milliliters/minute~4000 standard milliliters/minute.

Optionally, second adhesion layer include positioned at first the first face of adhesion layer the second adhesion material film and be located at the The third adhesion material film of the multiple-level stack of two adhesion material film top surfaces, the second adhesion material film and third adhere to material Expect to contain the first bonded atom, the second bonded atom and ruthenium atom in film, and the second bonding is former in the third adhesion material film For the atom percentage concentration of son less than the atom percentage concentration of the second bonded atom in the second mucous membrane material membrane, the third is viscous The atom percentage concentration of ruthenium atom is greater than the atom percentage concentration of ruthenium atom in the second adhesion material film, edge in enclosure material film On the direction of substrate surface, in third adhesion material film the atom percentage concentration of the second bonded atom successively lower and Ruthenium atom successively increases in third adhesion material film.

Optionally, the formation process of second adhesion layer includes: the second atom layer deposition process, the second atomic layer deposition The step of technique includes: to form the second adhesion material film using the second atomic layer deposition step；Form second adhesion material After film, the third adhesion material film of multiple-level stack is formed using multiple second atomic layer deposition step, every time the second atomic layer Deposition step forms one layer of third adhesion material film；The parameter of second atom layer deposition process includes: that temperature is 200 Celsius ~350 degrees Celsius of degree, pressure are 2 supports~5 supports；Second atomic layer deposition step includes: using third aeration process to institute It states in opening and is passed through tantalum presoma, part tantalum presoma is adsorbed on the first adhesion layer, forms the second precursor film；Described in formation After second precursor film, the unadsorbed tantalum presoma in opening sidewalls and bottom surface is removed using third air aspiration process；Institute After stating third air aspiration process, ruthenium presoma, the absorption of part ruthenium presoma are passed through into the opening using the 4th aeration process Second precursor film surface forms third precursor film；It is formed after third precursor film, not using the removal of the 4th air aspiration process With the ruthenium presoma of second forerunner's precursor reactant；After 4th air aspiration process, using the 5th aeration process into the opening It is passed through nitrogen presoma, part nitrogen presoma reacts to form adhesion material film with third precursor film；Form the adhesion material film Later, the nitrogen presoma not reacted with third precursor film is removed using the 5th air aspiration process；It is walked using the second atomic layer deposition The rapid adhesion material film for forming the second adhesion material film is the second adhesion material film, forms the using the second atomic layer deposition step The adhesion material film of three adhesion material films is third adhesion material film.

Optionally, the technological parameter for forming the second adhesion material film includes: the parameter packet of the third aeration process Include: tantalum presoma includes PDMAT, and the flow of tantalum presoma is 500 standard milliliters/minute~2000 standard milliliters/minute, third Duration of ventilation is 200 milliseconds~800 milliseconds；The parameter of third air aspiration process includes: that carrier gas includes argon gas, and third pumpdown time is 1000 milliseconds~3000 milliseconds, the flow of carrier gas is 2000 standard milliliters/minute~4000 standard milliliters/minute；4th ventilation The parameter of technique: including double ethyicydopentadi etanyf group rutheniums including ruthenium presoma, the flow of ruthenium presoma be 500 standard milliliters/point Four duration of ventilation of clock~2000, the is 200 milliseconds~800 milliseconds；It includes argon gas that the parameter of 4th air aspiration process, which includes: carrier gas, 4th duration of ventilation is 1000 milliseconds~3000 milliseconds, the flow of carrier gas be 2000 standard milliliters/minute~4000 standard milliliters/ Minute；It includes ammonia or nitrogen that the parameter of 5th aeration process, which includes: nitrogen source, the flow of the nitrogen source be 300 standard milliliters/ Minute~800 standard milliliters/minute, the time of the 5th ventilation are 500 milliseconds~1500 milliseconds；The parameter packet of 5th air aspiration process Include: carrier gas includes argon gas, and the time of the 5th pumping is 1000 milliseconds~3000 milliseconds, and 2000 standard milliliters of flow of carrier gas/point Clock~4000 standard milliliters/minute.

Optionally, first barrier layer include the first barrier material film and be located at the first barrier material film top surface it is more Contain the first bonded atom in the second barrier material film that layer heap is folded, the first barrier material film and the second barrier material film, And in the second barrier material film the first bonded atom atom percentage concentration less than the first key in the first barrier material film The atom percentage concentration of atom is closed, and along on the direction of substrate surface, first is bonded in each the second barrier material of layer film The atom percentage concentration of atom successively reduces.

Optionally, the formation process on first barrier layer includes: third atom layer deposition process, the third atomic layer The step of depositing operation includes: to form the first barrier material film using third atomic layer deposition step；Described first is formed to stop After material membrane, the second barrier material film of multiple-level stack is formed using multiple third atomic layer deposition step, each third is former Sublayer deposition step forms one layer of second barrier material film；The parameter of the third atom layer deposition process includes: that temperature is 200 Degree Celsius~350 degrees Celsius, pressure is 2 supports~5 supports；The step of third atom layer deposition process: using the 6th ventilation work Skill is passed through ruthenium presoma into the opening, and part ruthenium presoma is adsorbed on the first adhesion layer, forms the 4th precursor film；Institute After stating the 6th aeration process, removed using the 6th air aspiration process unadsorbed in the ruthenium presoma on the first adhesion layer；Described After six air aspiration process, nitrogen presoma is passed through into the opening using the 7th aeration process, before part nitrogen presoma and the 4th It drives body film and forms the first barrier material film；Formed after the first barrier material film, using the 7th air aspiration process removal not with The nitrogen presoma of 4th precursor film reaction；The barrier material of the first barrier material film is formed using third atomic layer deposition step Film is the first barrier material film, and third atomic layer deposition step is used to form the barrier material film of the second barrier material film as second Barrier material film.

Optionally, it includes: ruthenium that the technological parameter of the first barrier material film of formation, which includes: the parameter of the 6th aeration process, Presoma includes double ethyicydopentadi etanyf group rutheniums, the flow of ruthenium presoma be 500 standard milliliters/minute~2000 standard milliliters/ Minute, the 6th duration of ventilation is 200 milliseconds~800 milliseconds；It includes argon gas that the parameter of 6th air aspiration process, which includes: carrier gas, and the 6th Duration of ventilation is 1000 milliseconds~3000 milliseconds, the flow of carrier gas be 2000 standard milliliters/minute~4000 standard milliliters/point Clock；It includes ammonia and nitrogen that the parameter of 7th aeration process, which includes: nitrogen source, the flow of nitrogen source be 300 standard milliliters/minute~ 800 standard milliliters/minute, the 7th duration of ventilation are 500 milliseconds~1500 milliseconds；The parameter of 7th air aspiration process includes: carrier gas Including argon gas, the 7th pumpdown time is 1000 milliseconds~3000 milliseconds, and the flow of carrier gas is 2000 standard milliliters/minute~4000 Standard milliliters/minute.

Optionally, the formation process on second barrier layer includes: the 4th atom layer deposition process；4th atomic layer The step of depositing operation includes the third barrier film that multiple-level stack is formed using multiple 4th atomic layer deposition step, and every time the 4th Atomic layer deposition step forms one layer of third barrier film；The parameter of 4th atom layer deposition process includes: that temperature 200 is Celsius ~350 degrees Celsius of degree, pressure are 2 supports~5 supports, the number of the 4th atomic layer deposition step are as follows: 20 times~40 times；Described 4th is former Sublayer deposition step includes: that ruthenium presoma is passed through into the opening using the 8th aeration process, and part ruthenium presoma is adsorbed in The surface on first barrier layer forms third barrier film；It is formed after the third barrier film, is gone using the 8th air aspiration process Except the unadsorbed ruthenium presoma in the first barrier layer surface.

Optionally, it includes double ethyicydopentadi etanyf group rutheniums that the parameter of the 8th aeration process, which includes: ruthenium presoma, before ruthenium The flow for driving body is 500 standard milliliters/minute~2000 standard milliliters/minute, and the 8th duration of ventilation is 200 milliseconds~800 millis Second；The parameter of 8th air aspiration process includes: that carrier gas includes argon gas and helium, and the 8th pumpdown time is 1000 milliseconds~3000 Millisecond, the flow of argon gas are 2000 standard milliliters/minute~4000 standard milliliters/minute, and the flow of helium is 1000 standards milli Liter/min~3000 standard milliliters/minute.

The present invention also provides a kind of semiconductor structures, comprising: substrate has dielectric layer, the dielectric layer in the substrate It is interior that there is opening；Positioned at the first adhesion layer of the opening sidewalls and bottom surface, first adhesion layer includes opposite Contain the first bonded atom with the second face, first face and dielectric layer contact, the material on second face surface on one side；It is located at The barrier structure in second face of the first adhesion layer, the barrier structure include third face, and the third face and the second face paste are closed, And the material on third face surface contains the first bonded atom, also contains ruthenium atom in the barrier structure；It is opened positioned at described Interconnection structure in mouth inner barrier structure.

Optionally, the material of first adhesion layer includes tantalum nitride, and first bond ion is Nitrogen ion；Described The thickness of one adhesion layer are as follows: 20 angstroms~40 angstroms.

Optionally, the barrier structure includes: the first barrier layer and the second barrier layer on the first barrier layer, described Second face of barrier structure is the binding face on the first barrier layer and first the first face of adhesion layer；The material packet on first barrier layer Include: nitridation ruthenium, the material on second barrier layer includes ruthenium.

Optionally, the semiconductor structure further includes the second adherency between the first adhesion layer and the first barrier layer Layer；The material of second adhesion layer includes TaRuN；Second adhesion layer includes opposite fourth face and the 5th face, described 5th face and the third face paste are closed, and the fourth face and the second face paste are closed, the material of the fourth face and the 5th face surface Containing the first bonded atom, and the fourth face and the material on the second face surface also contain the second bonded atom, second key Conjunction atom is tantalum atom, and the material of the 5th face and third face surface also contains ruthenium atom；Second adhesion layer With a thickness of 20 angstroms~40 angstroms.

Compared with prior art, the technical solution of the embodiment of the present invention has the advantages that

In the forming method for the semiconductor structure that technical solution of the present invention provides, contain ruthenium atom in the barrier structure, So that the resistance of barrier structure is lower, be conducive to the performance for improving semiconductor devices.Also, formed the barrier structure it Before, the first adhesion layer is formed in the side wall and bottom surface of the opening.The second face and blocking due to first adhesion layer The first bonded atom is contained in the third face of structure so that the difference of third face and the second face joint place is smaller, then third face with The interfacial state in the second face is preferable, and the interfacial state of first face of the first adhesion layer and dielectric layer is preferable, therefore, barrier structure with Interfacial state between dielectric layer is preferable, is conducive to the performance for improving semiconductor devices.

Further, the barrier structure includes the first barrier layer and the second barrier layer on the first barrier layer.It is formed It after first adhesion layer, is formed before the first barrier layer, forms the second adhesion layer in second face of the first adhesion layer.Described The material of one adhesion layer includes: tantalum nitride, and the material of second adhesion layer includes TaRuN, and second adhesion layer includes phase Pair fourth face and the 5th face, the 5th face and three face pastes close, the fourth face and the second face paste are closed, the fourth face and the The surfacing in five faces also includes the first bonded atom, so that the 5th face and third face interface and fourth face and the second face The otherness of interface is smaller, and therefore, the interfacial state between the first barrier layer, the second adhesion layer and the first adhesion layer is preferable.And And the surfacing in third face and the 5th face also contains ruthenium atom, so that third face and the interfacial state in the 5th face further increase. And the fourth face and the surfacing in the second face also contain the second bonded atom, second bonded atom is tantalum atom, is made The interfacial state obtained between fourth face and the second face further increases, and therefore, second adhesion layer can further increase blocking Interfacial state between structure and dielectric layer is conducive to the performance for further increasing semiconductor devices.

Further, second adhesion layer includes the second adhesion material film and the multilayer heap at the top of the second adhesion material film Folded third adhesion material film.Due in the second adhesion material film and third adhesion material film contain the first bonded atom, Second bonded atom and ruthenium atom, and along the direction for deviating from substrate surface, the second bonded atom in third adhesion material film Atom percentage concentration successively lowers and the atom percentage concentration of ruthenium atom successively increases in third adhesion material film, therefore, Be conducive to improve the interfacial state between the second adhesion material film and third adhesion material film and adjacent third adhesion material film, And then be conducive to further increase the interfacial state between barrier structure and dielectric layer.

Further, first barrier layer include the first barrier material film and be located at the first barrier material film top surface it is more The material of the second folded barrier material film of layer heap, the first barrier material film and the second barrier material film includes nitridation ruthenium, and Along along the direction of substrate surface, the atom percentage concentration of the first bonded atom described in second barrier film materials by Layer reduces, so that the interfacial state between the second barrier material film and the first material membrane and adjacent second barrier material film Preferably, also, the interfacial state between the first adhesion layer and dielectric layer is preferable, therefore, is conducive to improve the first barrier layer and be situated between Interfacial state between matter layer, and then improve the performance of semiconductor devices.

Detailed description of the invention

Fig. 1 is a kind of structural schematic diagram of semiconductor structure；

Fig. 2 to Fig. 9 is the structural schematic diagram of each step of forming process of semiconductor structure in one embodiment of the invention.

Specific embodiment

As described in background, the performance for the semiconductor devices that the prior art is formed is poor.

Fig. 1 is a kind of structural schematic diagram of semiconductor structure.

Referring to FIG. 1, substrate 100, there is dielectric layer 101 in the substrate 100, there is opening in the dielectric layer 101 (not marked in figure)；Positioned at the opening sidewalls and the barrier structure of bottom surface 104；The barrier layer in the opening Interconnection structure 105 on 104.

In above-mentioned semiconductor structure, the material of the interconnection structure 105 includes copper, and the material of the dielectric layer 101 includes Silica, copper atom has high mobility, and the diffusion in silica is more accelerated.The barrier structure 104 is for stopping Copper atom diffuses in dielectric layer 101 and substrate 100 in interconnection structure 105, prevents copper atom to dielectric layer 101 and substrate 100 Performance impact.

Normally, the material of the barrier structure 104 contains tantalum, however, the resistance of the tantalum is about 15 Europe~30 Europe, That is: the resistance of the described tantalum is larger, so that the resistance for being formed by semiconductor structure is larger, is unfavorable for improving the electricity of semiconductor devices Learn performance.

A kind of method reducing semiconductor devices resistance include: using material of the material containing ruthenium as barrier structure 104, The resistance of ruthenium is about 7 Europe.Also, research also shows: nitridation ruthenium in amorphous state so that nitridation ruthenium to the barrier properties of copper atom compared with It is good, be conducive to the performance for improving semiconductor devices.

However, since the material of the dielectric layer 101 includes silica, nitrogenize the otherness of ruthenium and silica material compared with Greatly, so that the interfacial state between nitridation ruthenium and silica is poor, the performance of semiconductor devices is poor.

To solve the technical problem, the present invention provides a kind of forming methods of semiconductor structure, form the blocking Before structure, the first adhesion layer is formed in the side wall and bottom surface of the opening, and first adhesion layer includes opposite the Contain the first bonded atom with the second face, first face and dielectric layer contact, the material on second face surface on one side.It is described Barrier structure includes third face, and the third face and the second face paste are closed, and the first bond ion is contained in the third face, so that resistance The interfacial state kept off between structure and dielectric layer is preferable, to be conducive to improve the performance of semiconductor devices.

It is understandable to enable above-mentioned purpose of the invention, feature and beneficial effect to become apparent, with reference to the accompanying drawing to this The specific embodiment of invention is described in detail.

Fig. 2 to Fig. 9 is the structural schematic diagram of each step of forming process of semiconductor structure in one embodiment of the invention.

Referring to FIG. 2, providing substrate 200, there is initial medium layer 201 in the substrate 200.

In the present embodiment, the substrate 200 is silicon substrate.In other embodiments, the substrate can also serve as a contrast for germanium The semiconductor substrates such as bottom, silicon-Germanium substrate, silicon-on-insulator, germanium on insulator or sige-on-insulator.

In other embodiments, there is semiconductor devices, such as MOS transistor in the substrate.

In the present embodiment, the initial medium layer 201 is single layer structure, and the material of the initial medium layer 201 includes: Low-K dielectric material.

The low-K dielectric material refers to dielectric material of the relative dielectric constant less than 3.9.The low-K dielectric material is Porous material.

In the present embodiment, the material of the initial medium layer 201 includes: SiCOH.

In other embodiments, the initial medium layer is single layer structure, and the material of the initial medium layer includes: fluorine doped Silica (FSG), the silica (BSG) of boron-doping, the silica (PSG) of p-doped, boron-doping phosphorus silica (BPSG)；Alternatively, the initial medium layer is laminated construction, the initial medium layer includes: the stop-layer on base top surface And the low K dielectric layer on stop-layer.

Subsequent that interconnection structure is formed in the initial medium layer 201, the material of the initial medium layer 201 is low K Jie Material, the low-K dielectric material can reduce the capacitor between interconnection structure, can reduce interconnection structure in interconnection structure Time constant reduces the delay of circuit signal.

Subsequent that opening is formed in the initial medium layer 201, the opening can be dual damascene openings, can also be with For single Damascus opening.

It in the present embodiment, is that presenting a demonstration property of dual damascene openings illustrates with the opening, the dual damascene is opened Mouth includes: through-hole and the groove on through-hole.Specifically please refer to Fig. 3.

Referring to FIG. 3, the removal part initial medium layer 201, forms dielectric layer 202, has in the dielectric layer 202 Opening 203.

The depth-to-width ratio of the opening 203 is set according to process requirements.

The opening 203 includes: through-hole (not marking in figure) in the dielectric layer 202 and is located at the through-hole On groove (not marked in figure).

In the present embodiment, it is formed after the groove, forms the through-hole.In other embodiments, the ditch is formed Before slot, the through-hole is formed.

The forming step of the groove includes: that patterned first mask layer is formed on initial medium layer 201；With described First mask layer is exposure mask, etches the initial medium layer 201 and forms groove.

Using first mask layer as exposure mask, the technique for etching the initial medium layer 201 includes: dry etch process.

The depth-to-width ratio of the groove is set according to process requirements.

In the present embodiment, the material of first mask layer includes: silica, silicon nitride, photoresist or metal material, Wherein, metal material includes: TiN, TaN, WN.

The forming step of the through-hole includes: to be formed on the initial medium layer 201 with the bottom surface of part of trench Second mask layer, second mask layer expose the section bottom of the groove；Using second mask layer as exposure mask, etching The initial medium layer 201 forms through-hole until exposing the top surface of substrate 200.

Using second mask layer as exposure mask, the technique for etching the initial medium layer 201 includes: dry etch process.

The depth-to-width ratio of the through-hole is set according to process requirements.

In the present embodiment, the material of second mask layer includes: silica, silicon nitride, photoresist or metal material, Wherein, metal material includes: TiN, TaN, WN.

It is formed after the through-hole, first mask layer and second mask layer and part of the removal on dielectric layer 202 Second mask layer of channel bottom.

Referring to FIG. 4, forming the first adhesion layer 204 in the opening 203, first adhesion layer 204 includes opposite The first face 1 and the second face 2, first face 1 contacts with dielectric layer 202, and the material on 2 surface of the second face contains the first key Close atom.

The material of first adhesion layer 204 includes: tantalum nitride, and tantalum nitride is to copper atom in the interconnection structure being subsequently formed Blocking capability be greater than titanium nitride to the blocking capability of copper atom.Also, the interfacial state between tantalum nitride and dielectric layer 202 compared with It is good, it may be assumed that the interfacial state between the first face 1 and dielectric layer 202 is preferable, is conducive to the performance for improving semiconductor devices.

The material on 204 second face of the first adhesion layer, 2 surface contains the first bonded atom, and first bonded atom is Nitrogen-atoms.

The formation process of first adhesion layer 204 includes: the first atom layer deposition process, first atomic layer deposition The step of technique includes the first adhesive film that multiple-layer overlapped is formed using multiple first atomic layer deposition step, every time the first atom Layer deposition steps form one layer of first adhesion material film.

The parameter of first atom layer deposition process includes: that temperature is 200 degrees Celsius~350 degrees Celsius, and pressure is 2 supports ~5 supports, the number of the first atomic layer deposition step are as follows: 20 times~40 times.

First atomic layer deposition step includes: that tantalum presoma, part are passed through into the opening using the first aeration process Tantalum presoma is adsorbed in side wall and the bottom of opening, forms the first precursor film；It is formed after first precursor film, is used First air aspiration process removes the unadsorbed tantalum presoma in opening sidewalls and bottom surface；After first air aspiration process, adopt Nitrogen presoma is passed through into the opening with the second aeration process, part nitrogen presoma reacts to form first with the first precursor film Adhesion material film；It is formed after the first adhesion material film, is not reacted with the first precursor film using the removal of the second air aspiration process Nitrogen presoma.

The parameter of first aeration process includes: that tantalum presoma includes PDMAT, and the flow of tantalum presoma is 500 standards Ml/min~2000 standard milliliters/minute, the first duration of ventilation are 200 milliseconds~800 milliseconds；First air aspiration process Parameter include: carrier gas include argon gas, the first pumpdown time is 1000 milliseconds~3000 milliseconds, and the flow of carrier gas is 2000 standards Ml/min~4000 standard milliliters/minute；It includes ammonia or nitrogen that the parameter of second aeration process, which includes: nitrogen presoma, The flow of nitrogen presoma be 300 standard milliliters/minute~800 standard milliliters/minute, the second duration of ventilation be 500 milliseconds~ 1500 milliseconds；The parameter of second air aspiration process includes: that carrier gas includes argon gas, and the time of the second pumping is 1000 milliseconds~3000 millis Second, the flow of carrier gas is 2000 standard milliliters/minute~4000 standard milliliters/minute.

On the one hand first adhesion layer 204 effect includes: that first adhesion layer 204, which is used to improving, to be subsequently formed Interfacial state between barrier structure and dielectric layer 202；On the other hand, first adhesion layer 204 is also used to prevent to be subsequently formed Interconnection structure in copper atom diffuse in dielectric layer 202, it is advantageously ensured that the electric isolution performance of dielectric layer 202.

First adhesion layer, 204 second face 2 is bonded with the fourth face for the second adhesion layer being subsequently formed, the fourth face The material on surface also contains the first bonded atom, so that the second face 2 and the interfacial state of fourth face are preferable, is conducive to improve semiconductor The performance of device.

Referring to FIG. 5, forming the second adhesion layer 205 on 2 surface of the second face, second adhesion layer 205 includes phase Pair fourth face 4 and the 5th face 5, the fourth face 4 be bonded with the second face 2, the material of the fourth face 4 and 5 surface of the 5th face Also contain the first bonded atom.

In the present embodiment, it is formed after second adhesion layer 205, in 5 table of the 5th face of second adhesion layer 205 Face forms barrier structure.

In other embodiments, the second adhesion layer is not formed, is directly formed and is stopped on the second face surface of the first adhesion layer Structure.

The effect of second adhesion layer 205 includes: on the one hand, after second adhesion layer 205 is for further improving Interfacial state between the continuous barrier structure and dielectric layer 202 formed；On the other hand, second adhesion layer 205 is also used to prevent The copper atom in interconnection structure being subsequently formed diffuses in dielectric layer 202, be conducive to further ensure that the electricity of dielectric layer 202 every From performance.

The surfacing of the fourth face 4 also contains the first bonded atom, so that the interfacial state of fourth face 4 and the second face 2 Preferably, be conducive to improve the interfacial state between the second adhesion layer 205 and the first adhesion layer 204.

The material of second adhesion layer 205 includes: TaRuN, and second adhesion layer 205 is also former containing the second bonding Son, second bonded atom is tantalum atom, and therefore first adhesion layer 204 is also conducive to containing the second bonded atom Further increase the interfacial state between the second adhesion layer 205 and the first adhesion layer 204.

And subsequent the first barrier layer formed at the top of the second adhesion layer 205 also contains other than containing the first bonded atom There is ruthenium atom, so that the interfacial state between the second adhesion layer 205 and the first barrier layer is preferable.And second adhesion layer 205 with The interfacial state between interfacial state and the first adhesion layer 204 and dielectric layer 202 between first adhesion layer 204 is preferable, so that Interfacial state between first barrier layer and dielectric layer 202 is preferable.Interfacial state between first barrier layer and dielectric layer 202 is determined Determine the interfacial state between barrier structure and dielectric layer 202, therefore, interfacial state between the barrier structure and dielectric layer 202 compared with It is good, be conducive to the performance for improving semiconductor devices.

In the present embodiment, second adhesion layer 205 includes the second adherency material positioned at the first adhesion layer top surface Expect the third adhesion material film of film and the multiple-level stack positioned at the second adhesion material film top surface, the second adhesion material film With the first bonded atom, the second bonded atom and ruthenium atom are all had in third adhesion material film.And along away from 200 surface of substrate Direction on, the atom percentage concentration of the second bonded atom described in the second adhesion material film successively reduces, the ruthenium The atom percentage concentration of atom successively increases, so that between the second adhesion material film and third adhesion material film and adjacent Interfacial state between third adhesion material film is preferable, be conducive to improve between the second adhesion material and third adhesion material film, with And the interfacial state between adjacent third adhesion material film is preferable, to be conducive to improve the performance of the second adhesion layer 205.

In other embodiments, the atomic percent in the third adhesion material film with second bonded atom is dense Spend it is identical, in the third adhesion material film with the ruthenium atom atom percentage concentration it is identical.

In the present embodiment, the formation process of second adhesion layer 205 includes the second atom layer deposition process, and second is former The step of sublayer depositing operation includes: to form the second adhesion material film using the second atomic layer deposition step；Form described second After adhesion material film, the third adhesion material film of multiple-level stack is formed using multiple second atomic layer deposition step, every time the Two atomic layer deposition steps form one layer of third adhesion material film.

In the present embodiment, the parameter of second atom layer deposition process includes: that temperature is taken the photograph for 200 degrees Celsius~350 Family name's degree, pressure are 2 supports~5 supports.

In the present embodiment, second atomic layer deposition step include: using third aeration process into the opening It is passed through tantalum presoma, part tantalum presoma is adsorbed on the first adhesion layer, forms the second precursor film；Form second forerunner After body film, the unadsorbed tantalum presoma in opening sidewalls and bottom surface is removed using third air aspiration process；The third is taken out After gas technique, ruthenium presoma is passed through into the opening using the 4th aeration process, part ruthenium presoma adsorbs the second forerunner Body film surface forms third precursor film；Formed after third precursor film, using the removal of the 4th air aspiration process not with second before Drive the ruthenium presoma of precursor reactant；After 4th air aspiration process, before being passed through nitrogen into the opening using the 5th aeration process Body is driven, part nitrogen presoma reacts to form the second adhesive film with third precursor film；It is formed after second adhesive film, is used 5th air aspiration process removes the nitrogen presoma not reacted with third precursor film；Second is formed using the second atomic layer deposition step The adhesion material film of adhesion material film is the second adhesion material film, forms third adhesion material using the second atomic layer deposition step The adhesion material film of film is third adhesion material film.

In the present embodiment, the technological parameter for forming second adhesive film includes: the parameter of the third aeration process It include: tantalum presoma include PDMAT, the flow of tantalum presoma is 500 standard milliliters/minute~2000 standard milliliters/minute, the Three duration of ventilation are 200 milliseconds~800 milliseconds；The parameter of third air aspiration process includes: that carrier gas includes argon gas, third pumpdown time It is 1000 milliseconds~3000 milliseconds, the flow of carrier gas is 2000 standard milliliters/minute~4000 standard milliliters/minute；Four-way It includes double ethyicydopentadi etanyf group rutheniums that the parameter of gas technique, which includes: ruthenium presoma, the flow of ruthenium presoma be 500 standard milliliters/ Minute~2000, the 4th duration of ventilation is 200 milliseconds~800 milliseconds；It includes argon that the parameter of 4th air aspiration process, which includes: carrier gas, Gas, the 4th pumpdown time are 1000 milliseconds~3000 milliseconds, and the flow of carrier gas is 2000 standard milliliters/minute~4000 standards milli Liter/min；The parameter of 5th aeration process includes: that nitrogen source includes ammonia or nitrogen, and the flow of the nitrogen source is 300 standards milli Liter/min~800 standard milliliters/minute, the time of the 5th ventilation is 500 milliseconds~1500 milliseconds；The ginseng of 5th air aspiration process Number includes: that carrier gas includes argon gas, and the time of the 5th pumping is 1000 milliseconds~3000 milliseconds, the flow 2000 standard milli of carrier gas Liter/min~4000 standard milliliters/minute.

It is subsequent to form barrier structure on the 5th face surface of the second adhesion layer 205.

In the present embodiment, the barrier structure include: positioned at the 5th face 5 of the second adhesion layer 205 the first barrier layer and The second barrier layer on the first barrier layer, the barrier structure have third face.In the present embodiment, the third face is The binding face on the first barrier layer and the 5th face 5.

In other embodiments, the second adhesion layer is not formed, the third face is the first barrier layer to be bonded with the second face Face.The forming step of the barrier structure specifically please refers to Fig. 6 to Fig. 7.

Referring to FIG. 6, forming the first barrier layer 206, first barrier layer in the 5th face 5 of the second adhesion layer 205 206 include third face 3, and the material on 3 surface of third face contains the first bonded atom, contains in first barrier layer 206 Ruthenium atom.

The material on first barrier layer 206 includes: nitridation ruthenium, and the material on 3 surface of third face contains the first bonding Atom, first bonded atom is nitrogen-atoms, so that third face 3 and the difference of 5 interface of the 5th face are smaller, therefore, favorably Interfacial state between raising third face 3 and the 5th face 5.

Also, the material on the third face 3 and 5 surface of the 5th face also contains ruthenium atom, so that third face 3 and the 5th face 5 The difference of interface further decreases, and therefore, is conducive to further increase the interfacial state between third face 3 and the 5th face 5.

In addition, nitridation ruthenium is amorphous state, therefore, material of the nitridation ruthenium as the first barrier layer 206 is selected, so that the first resistance Barrier 206 is stronger to the blocking capability of atom in the interconnection structure being subsequently formed, then the atom is not easy to diffuse to dielectric layer 202 It is interior, so that the performance of 202 isolation of semiconductor different components of dielectric layer is stronger.

Moreover, the resistance of nitridation ruthenium is smaller, therefore, using RuN as the first barrier layer 206, partly led so that being formed by The resistance of body device is smaller, is conducive to the electric property for improving semiconductor devices.

First barrier layer 206 is including the first barrier material film and is located at the first barrier material film top surface multilayer heap The second folded barrier material film.

The formation process on first barrier layer 206 includes: third atom layer deposition process, the third atomic layer deposition The step of technique includes: to form the first barrier material film using third atomic layer deposition step；Form first barrier material After film, the second barrier material film of multiple-level stack, each third atomic layer are formed using multiple third atomic layer deposition step Deposition step forms one layer of second barrier material film.

In the present embodiment, the parameter of the third atom layer deposition process includes: that temperature is taken the photograph for 200 degrees Celsius~350 Family name's degree, pressure are 2 supports~5 supports.

The step of third atom layer deposition process: ruthenium forerunner is passed through into the opening using the 6th aeration process Body, part ruthenium presoma are adsorbed on the first adhesion layer, form the 4th precursor film；After 6th aeration process, use 6th air aspiration process removes unadsorbed in the ruthenium presoma on the first adhesion layer；After 6th air aspiration process, using the 7th Aeration process is passed through nitrogen presoma into the opening, and part nitrogen presoma and the 4th precursor film form barrier material film；Shape After the barrier material film, the nitrogen presoma not reacted with the 4th precursor film is removed using the 7th air aspiration process；Using The barrier material film that third atomic layer deposition step forms the first barrier material film is the first barrier material film, using third atom The barrier material film that layer deposition steps form the second barrier material film is the second barrier material film.

In the present embodiment, the technological parameter for forming the first barrier material film includes: the 6th aeration process It includes double ethyicydopentadi etanyf group rutheniums that parameter, which includes: ruthenium presoma, the flow of ruthenium presoma be 500 standard milliliters/minute~ 2000 standard milliliters/minute, the 6th duration of ventilation are 200 milliseconds~800 milliseconds；The parameter of 6th air aspiration process includes: carrier gas Including argon gas, the 6th duration of ventilation is 1000 milliseconds~3000 milliseconds, and the flow of carrier gas is 2000 standard milliliters/minute~4000 Standard milliliters/minute；The parameter of 7th aeration process includes: that nitrogen source includes ammonia or nitrogen, and the flow of nitrogen source is 300 standards Ml/min~800 standard milliliters/minute, the 7th duration of ventilation are 500 milliseconds~1500 milliseconds；The ginseng of 7th air aspiration process Number includes: that carrier gas includes argon gas, and the 7th pumpdown time is 1000 milliseconds~3000 milliseconds, and the flow of carrier gas is 2000 standards milli Liter/min~4000 standard milliliters/minute.

In the present embodiment, there is the first bonded atom in the first barrier material film and the second barrier material film, and The atom percentage concentration of the first bonded atom is less than the first bonding in the first barrier material film in the second barrier material film The atom percentage concentration of atom, and along on the direction on 200 surface of substrate, first is bonded in each the second barrier material of layer film The atom percentage concentration of atom successively reduces, so that the first barrier material film and the second barrier material film and adjacent Difference at second barrier material membrane interface is smaller, be conducive to improve the first barrier material film and the second barrier material film, And the interfacial state between adjacent second barrier material film, be conducive to the performance for improving the first barrier layer 206.

In other embodiments, the atom percentage concentration of the first bonded atom is identical in the first barrier material film.

It is former in the interconnection structure that first barrier layer 206 and the second barrier layer being subsequently formed are used to stop to be subsequently formed Son diffuses in dielectric layer 202, influences dielectric layer 202 and is electrically isolated performance.

Referring to FIG. 7, forming the second barrier layer 207 on first barrier layer 206.

The material on second barrier layer 207 includes: ruthenium.The formation process on second barrier layer 207 includes: the 4th original Sublayer depositing operation；The step of four atom layer deposition process, is more including being formed using multiple 4th atomic layer deposition step The folded third barrier material film of layer heap, the 4th atomic layer deposition step forms one layer of third barrier material film every time.

In the present embodiment, the parameter of the 4th atom layer deposition process includes: that temperature 200 degrees Celsius~350 is Celsius Degree, pressure are 2 supports~5 supports, the number of the 4th atomic layer deposition step are as follows: 20 times~40 times；The 4th atomic layer deposition step It suddenly include: that ruthenium presoma is passed through into the opening using the 8th aeration process, part ruthenium presoma is adsorbed in first resistance The surface of barrier forms third barrier material film；It is formed after the third barrier material film, is removed using the 8th air aspiration process The unadsorbed ruthenium presoma in the first barrier layer surface.

In the present embodiment, it includes double ethyicydopentadi etanyf groups that the parameter of the 8th aeration process, which includes: ruthenium presoma, Ruthenium, the flow of ruthenium presoma are 500 standard milliliters/minute~2000 standard milliliters/minute, and the 8th duration of ventilation is 200 milliseconds ~800 milliseconds；The parameter of 8th air aspiration process includes: that carrier gas includes argon gas and helium, and the 8th pumpdown time is 1000 millis Second~3000 milliseconds, the flow of argon gas is 2000 standard milliliters/minute~4000 standard milliliters/minute, and the flow of helium is 1000 standard milliliters/minute~3000 standard milliliters/minute.

Ruthenium atom is contained in second barrier layer 207 and 206 interface of the first barrier layer, so that the second barrier layer 207 The difference of interface between the first barrier layer 206 is smaller, is conducive to improve the second barrier layer 207 and the first barrier layer 206 Between interfacial state, and then be conducive to improve semiconductor devices performance.

The original in interconnection structure that second barrier layer 207 and the first barrier layer 206 are used to stop to be subsequently formed jointly Son prevents the atom from diffusing to dielectric layer 202, influences the electric property between 202 isolation of semiconductor different components of dielectric layer.

Also, using material of the ruthenium as the second barrier layer 207, on the one hand can improve the second barrier layer 207 with it is subsequent Interfacial state between the interconnection structure of formation.Meanwhile the resistance of ruthenium is smaller, then the resistance for being formed by semiconductor devices is smaller, Be conducive to improve the electric property of semiconductor devices.

It is formed after second barrier layer 207, forms interconnection structure in the opening 203.The interconnection structure packet It includes: the seed layer on the second barrier layer 207 in the opening 203 and the metal layer in seed layer.Specifically please refer to Fig. 8 to Fig. 9.

Referring to FIG. 8, forming seed layer 208 on the second barrier layer 207 in 203 (see Fig. 7) of the opening.

The seed layer 208 is used to be subsequently formed the nucleus of metal layer, and as it is subsequent formed using electroplating technology it is described The electrode of metal layer.

The material of the seed layer 208 includes: copper.The formation process of the seed layer 208 includes: sputtering technology.It is described The temperature of sputtering technology includes: 850 degrees Celsius~950 degrees Celsius.

In the present embodiment, the material on second barrier layer 207 is ruthenium, and the fusing point of ruthenium is higher, so that in the sputtering In technical process, phase does not change, then the second barrier layer 207 is preferable to the barrier properties of seed layer.

Referring to FIG. 9, forming metal layer 209 in the seed layer 208 in 203 (see Fig. 8) of the opening.

The material of the metal layer 209 includes copper.The formation process of the metal layer 209 includes electroplating technology.

Correspondingly, the present embodiment also provide it is a kind of semiconductor structure is formed by using the above method, please continue to refer to figure 9, comprising:

Substrate 200 has dielectric layer 202 in the substrate 200, has 203 (see Fig. 8) of opening in the dielectric layer；

Positioned at the first adhesion layer 204 of opening 203 side walls and bottom surface, first adhesion layer 204 includes phase Pair the first face 1 and the second face 2, first face 1 contacts with dielectric layer 202, and the material on 2 surface of the second face contains first Bonded atom；

Barrier structure positioned at 2 surface of the first 204 second face of adhesion layer, the barrier structure include third face 3, and described Three faces 3 are bonded with the second face 2, and the material on 3 surface of third face contains the first bonded atom, also contains in the barrier structure There is ruthenium atom.

Interconnection structure 209 in 203 inner barrier structures of the opening.

The material of first adhesion layer 206 includes: tantalum nitride；The thickness of first adhesion layer are as follows: 20 angstroms~40 angstroms.

The barrier structure includes: the first barrier layer 206 and the second barrier layer 207 on the first barrier layer 206, institute The third face 3 for stating barrier structure is the binding face in 204 second face 2 of the first barrier layer 206 and the first adhesion layer.

The material on first barrier layer 206 includes: nitridation ruthenium.The material on second barrier layer 207 includes ruthenium.

The semiconductor structure further include: the second barrier layer between the first adhesion layer 204 and the first barrier layer 206 205。

The material of second adhesion layer 205 includes: TaRuN；Second adhesion layer 205 includes opposite fourth face 4 With the 5th face 5, the 5th face 5 is bonded with the third face 3, and the fourth face 4 is bonded with the second face 2,4 He of fourth face The first bonded atom is also contained in 5th face 5, and the material on 2 surface of the fourth face 4 and the second face also includes the second bonded atom, Second bonded atom is tantalum atom, and the material on the 5th face and third face surface also contains ruthenium atom.

Second adhesion layer with a thickness of 20 angstroms~40 angstroms.

Although present disclosure is as above, present invention is not limited to this.Anyone skilled in the art are not departing from this It in the spirit and scope of invention, can make various changes or modifications, therefore protection scope of the present invention should be with claim institute Subject to the range of restriction.

Claims (19)

1. a kind of forming method of semiconductor structure characterized by comprising

Substrate is provided, there is dielectric layer in the substrate, there is opening in the dielectric layer；

Form the first adhesion layer in the side wall and bottom surface of the opening, first adhesion layer include opposite the first face and Second face, first face are contacted with dielectric layer, and the material on second face surface contains the first bonded atom；

Barrier structure is formed on the second face surface of first adhesion layer, the barrier structure includes third face, the third Face and the second face paste are closed, and the material on third face surface contains the first bonded atom, also contains ruthenium in the barrier structure Atom；

It is formed after the barrier structure, forms interconnection structure in the opening.

2. the forming method of semiconductor structure as described in claim 1, which is characterized in that the material packet of first adhesion layer Tantalum nitride is included, first bonded atom is nitrogen-atoms.

3. the forming method of semiconductor structure as claimed in claim 2, which is characterized in that the barrier structure includes the first resistance Barrier and the second barrier layer on the first barrier layer, the third face of the barrier structure are the first barrier layer and the second face Binding face.

4. the forming method of semiconductor structure as claimed in claim 3, which is characterized in that the material packet on first barrier layer Nitridation ruthenium is included, the material on second barrier layer includes ruthenium.

5. the forming method of semiconductor structure as claimed in claim 2, which is characterized in that formed first adhesion layer it Afterwards, it is formed before barrier structure, the forming method further include: form the second adhesion layer in the first adherency layer surface；Institute The material for stating the second adhesion layer includes TaRuN；Second adhesion layer includes opposite fourth face and the 5th face, the 5th face It is closed with third face paste, the fourth face and the second face paste are closed, and the material on the fourth face and the 5th face surface also contains the first key Atom is closed, and the fourth face and the material on the second face surface also contain the second bonded atom, second bonded atom is tantalum The material on atom, the 5th face and third face surface also contains the ruthenium atom.

6. the forming method of semiconductor structure as claimed in claim 2, which is characterized in that the formation work of first adhesion layer Skill includes the first atom layer deposition process, includes using multiple first atomic layer deposition the step of first atom layer deposition process Product step forms the first adhesion material film of multiple-layer overlapped, and the first atomic layer deposition step forms one layer of first adhesion material every time Film；The parameter of first atom layer deposition process: being 200 degrees Celsius~350 degrees Celsius including temperature, and pressure is 2 support~5 Support, the number of the first atomic layer deposition step are as follows: 20 times~40 times；First atomic layer deposition step includes: using the first ventilation Technique is passed through tantalum presoma into the opening, and part tantalum presoma is adsorbed in side wall and the bottom of opening, forms the first forerunner Body film；It is formed after first precursor film, is removed using the first air aspiration process unadsorbed in opening sidewalls and bottom surface Tantalum presoma；After first air aspiration process, nitrogen presoma, part are passed through into the opening using the second aeration process Nitrogen presoma reacts to form the first adhesion material film with the first precursor film；It is formed after the first adhesion material film, using second Air aspiration process removes the nitrogen presoma not reacted with the first precursor film.

7. the forming method of semiconductor structure as claimed in claim 6, which is characterized in that the parameter of first aeration process It include: tantalum presoma include PDMAT, the flow of tantalum presoma is 500 standard milliliters/minute~2000 standard milliliters/minute, the One duration of ventilation is 200 milliseconds~800 milliseconds；The parameter of first air aspiration process includes: that carrier gas includes argon gas, the first pumping Time is 1000 milliseconds~3000 milliseconds, and the flow of carrier gas is 2000 standard milliliters/minute~4000 standard milliliters/minute；The It includes ammonia or nitrogen that the parameter of two aeration process, which includes: nitrogen presoma, the flow of nitrogen presoma be 300 standard milliliters/point Clock~800 standard milliliters/minute, the second duration of ventilation are 500 milliseconds~1500 milliseconds；The parameter of second air aspiration process includes: Carrier gas includes argon gas, and the time of the second pumping is 1000 milliseconds~3000 milliseconds, and the flow of carrier gas is 2000 standard milliliters/minute ~4000 standard milliliters/minute.

8. the forming method of semiconductor structure as claimed in claim 5, which is characterized in that second adhesion layer includes being located at The third adhesion material film of the second adhesion material film in the first face and the multiple-level stack positioned at the second adhesion material film top surface, Contain the first bonded atom, the second bonded atom and ruthenium atom in the second adhesion material film and third adhesion material film, and The atom percentage concentration of the second bonded atom is less than the second bonding in the second adhesion material film in the third adhesion material film The atom percentage concentration of atom, the atom percentage concentration of ruthenium atom is greater than the second adherency material in the third adhesion material film The atom percentage concentration for expecting ruthenium atom in film, along on the direction of substrate surface, second is bonded in third adhesion material film The atom percentage concentration of atom successively lowers and the atom percentage concentration of ruthenium atom successively increases in third adhesion material film Add.

9. the forming method of semiconductor structure as claimed in claim 8, which is characterized in that the formation work of second adhesion layer The step of skill includes: the second atom layer deposition process, the second atom layer deposition process includes: using the second atomic layer deposition step Form the second adhesion material film；It is formed after the second adhesion material film, is formed using multiple second atomic layer deposition step The third adhesion material film of multiple-level stack, the second atomic layer deposition step forms one layer of third adhesion material film every time；Described The parameter of two atom layer deposition process includes: that temperature is 200 degrees Celsius~350 degrees Celsius, and pressure is 2 supports~5 supports；Described second Atomic layer deposition step includes: that tantalum presoma, the absorption of part tantalum presoma are passed through into the opening using third aeration process In on the first adhesion layer, the second precursor film is formed；It is formed after second precursor film, is removed using third air aspiration process The unadsorbed tantalum presoma in opening sidewalls and bottom surface；After the third air aspiration process, using the 4th aeration process to Ruthenium presoma is passed through in the opening, part ruthenium presoma adsorbs the second precursor film surface, forms third precursor film；It is formed After third precursor film, the not ruthenium presoma with second forerunner's precursor reactant is removed using the 4th air aspiration process；Described 4th takes out After gas technique, nitrogen presoma, part nitrogen presoma and third presoma are passed through into the opening using the 5th aeration process Film reaction forms adhesion material film；Formed after the adhesion material film, using the 5th air aspiration process removal not with third forerunner The nitrogen presoma of body film reaction；The second atomic layer deposition step is used to form the adhesion material film of the second adhesion material film as second Adhesion material film uses the second atomic layer deposition step to form the adhesion material film of third adhesion material film as third adhesion material Film.

10. the forming method of semiconductor structure as claimed in claim 9, which is characterized in that form second adhesion material It include: tantalum presoma includes PDMAT, the flow of tantalum presoma that the technological parameter of film, which includes: the parameter of the third aeration process, For 500 standard milliliters/minute~2000 standard milliliters/minute, third duration of ventilation is 200 milliseconds~800 milliseconds；Third pumping The parameter of technique includes: that carrier gas includes argon gas, and third pumpdown time is 1000 milliseconds~3000 milliseconds, and the flow of carrier gas is 2000 Standard milliliters/minute~4000 standard milliliters/minute；The parameter of 4th aeration process includes: that ruthenium presoma includes double ethyl rings Pentadienyl ruthenium, the flow of ruthenium presoma are that 500 standard milliliters/minute~2000, the, four duration of ventilation is 200 milliseconds~800 Millisecond；It includes argon gas that the parameter of 4th air aspiration process, which includes: carrier gas, and the 4th pumpdown time is 1000 milliseconds~3000 milliseconds, is carried The flow of gas is 2000 standard milliliters/minute~4000 standard milliliters/minute；The parameter of 5th aeration process includes: nitrogen source packet Ammonia or nitrogen are included, the flow of the nitrogen source is 300 standard milliliters/minute~800 standard milliliters/minute, the 5th ventilation Time is 500 milliseconds~1500 milliseconds；It includes argon gas that the parameter of 5th air aspiration process, which includes: carrier gas, the 5th pumping time be 1000 milliseconds~3000 milliseconds, 2000 standard milliliters of flow/minute~4000 standard milliliters/minute of carrier gas.

11. the forming method of semiconductor structure as claimed in claim 4, which is characterized in that first barrier layer includes the One barrier material film and the second barrier material film positioned at the first barrier material film top surface multiple-level stack, described first stops Contain the first bonded atom, and the first bonded atom in the second barrier material film in material membrane and the second barrier material film Atom percentage concentration less than the first bonded atom in the first barrier material film atom percentage concentration, and along deviate from substrate table On the direction in face, the atom percentage concentration of the first bonded atom is successively reduced in each the second barrier material of layer film.

12. the forming method of semiconductor structure as claimed in claim 11, which is characterized in that the formation on first barrier layer The step of technique includes: third atom layer deposition process, the third atom layer deposition process includes: using third atomic layer deposition Product step forms the first barrier material film；It is formed after the first barrier material film, is walked using multiple third atomic layer deposition Rapid the second barrier material film for forming multiple-level stack, each third atomic layer deposition step form one layer of second barrier material film； The parameter of the third atom layer deposition process includes: that temperature is 200 degrees Celsius~350 degrees Celsius, and pressure is 2 supports~5 supports；Institute The step of stating third atom layer deposition process: ruthenium presoma is passed through into the opening using the 6th aeration process, before the ruthenium of part It drives body to be adsorbed on the first adhesion layer, forms the 4th precursor film；After 6th aeration process, using the 6th air aspiration process It removes unadsorbed in the ruthenium presoma on the first adhesion layer；After 6th air aspiration process, using the 7th aeration process to institute It states and is passed through nitrogen presoma in opening, part nitrogen presoma and the 4th precursor film form barrier material film；Form the blocking material After expecting film, the nitrogen presoma not reacted with the 4th precursor film is removed using the 7th air aspiration process；Using third atomic layer deposition The barrier material film that product step forms the first barrier material film is the first barrier material film, using third atomic layer deposition step shape Barrier material film at the second barrier material film is the second barrier material film.

13. the forming method of semiconductor structure as claimed in claim 12, which is characterized in that form the first barrier material film Technological parameter includes: that the parameter of the 6th aeration process includes: that ruthenium presoma includes double ethyicydopentadi etanyf group rutheniums, ruthenium forerunner The flow of body is 500 standard milliliters/minute~2000 standard milliliters/minute, and the 6th duration of ventilation is 200 milliseconds~800 milliseconds； It includes argon gas that the parameter of 6th air aspiration process, which includes: carrier gas, and the 6th pumpdown time is 1000 milliseconds~3000 milliseconds, the stream of carrier gas Amount is 2000 standard milliliters/minute~4000 standard milliliters/minute；It includes ammonia that the parameter of 7th aeration process, which includes: nitrogen source, Or nitrogen, the flow of nitrogen source are 300 standard milliliters/minute~800 standard milliliters/minute, the 7th duration of ventilation is 500 milliseconds ~1500 milliseconds；It includes argon gas that the parameter of 7th air aspiration process, which includes: carrier gas, and the 7th pumpdown time is 1000 milliseconds~3000 millis Second, the flow of carrier gas is 2000 standard milliliters/minute~4000 standard milliliters/minute.

14. the forming method of semiconductor structure as claimed in claim 4, which is characterized in that the formation on second barrier layer Technique includes: the 4th atom layer deposition process；The step of four atom layer deposition process includes using multiple 4th atom Layer deposition steps form the third barrier material film of multiple-level stack, and the 4th atomic layer deposition step forms one layer of third and stops every time Material membrane；The parameter of 4th atom layer deposition process includes: 200 degrees Celsius~350 degrees Celsius of temperature, 2 support~5 of pressure Support, the number of the 4th atomic layer deposition step are 20 times~40 times；4th atomic layer deposition step includes: logical using the 8th Gas technique is passed through ruthenium presoma into the opening, and the surface that part ruthenium presoma is adsorbed in first barrier layer forms third Barrier material film；It is formed after the third barrier material film, is removed using the 8th air aspiration process unadsorbed in the first barrier layer The ruthenium presoma on surface.

15. the forming method of semiconductor structure as claimed in claim 14, which is characterized in that the ginseng of the 8th aeration process Number includes: that ruthenium presoma includes double ethyicydopentadi etanyf group rutheniums, and the flow of ruthenium presoma is 500 standard milliliters/minute~2000 Standard milliliters/minute, the 8th duration of ventilation are 200 milliseconds~800 milliseconds；The parameter of 8th air aspiration process includes: carrier gas Including argon gas and helium, the 8th pumpdown time is 1000 milliseconds~3000 milliseconds, and the flow of argon gas is 2000 standard milliliters/minute ~4000 standard milliliters/minute, the flow of helium are 1000 standard milliliters/minute~3000 standard milliliters/minute.

16. a kind of semiconductor structure characterized by comprising

Substrate has dielectric layer in the substrate, has opening in the dielectric layer；

Positioned at the first adhesion layer of the opening sidewalls and bottom surface, first adhesion layer includes opposite the first face and Two faces, first face are contacted with dielectric layer, and the material on second face surface contains the first bonded atom；

Barrier structure positioned at second face of the first adhesion layer, the barrier structure include third face, the third face and the Two face pastes are closed, and the material on third face surface contains the first bonded atom, also contains ruthenium atom in the barrier structure；

Interconnection structure in the opening inner barrier structure.

17. semiconductor structure as claimed in claim 16, which is characterized in that the material of first adhesion layer includes nitridation Tantalum, first bond ion are Nitrogen ion；The thickness of first adhesion layer are as follows: 20 angstroms~40 angstroms.

18. semiconductor structure as claimed in claim 17, which is characterized in that the barrier structure include: the first barrier layer and The second barrier layer on the first barrier layer, the third face of the barrier structure are the first barrier layer and the first adhesion layer second The binding face in face；The material on first barrier layer includes: nitridation ruthenium, and the material on second barrier layer includes ruthenium.

19. semiconductor structure as claimed in claim 18, which is characterized in that the semiconductor structure further include: be located at first The second adhesion layer between adhesion layer and the first barrier layer；The material of second adhesion layer includes TaRuN；Second adherency Layer includes opposite fourth face and the 5th face, and the 5th face and the third face paste are closed, and the fourth face and the second face paste are closed, The fourth face and the material on the 5th face surface also contain the first bonded atom, and the material of the fourth face and the second face surface It also include the second bonded atom, second bonded atom is tantalum atom, and ruthenium atom is also contained in the 5th face and third face；Institute State the second adhesion layer with a thickness of 20 angstroms~40 angstroms.