CN100490081C - Grid dielectric layer and its formation method - Google Patents
Grid dielectric layer and its formation method Download PDFInfo
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- CN100490081C CN100490081C CNB2005100655911A CN200510065591A CN100490081C CN 100490081 C CN100490081 C CN 100490081C CN B2005100655911 A CNB2005100655911 A CN B2005100655911A CN 200510065591 A CN200510065591 A CN 200510065591A CN 100490081 C CN100490081 C CN 100490081C
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Abstract
The invention makes a plasma processing art on a substrate to form a dielectric layer structure on the substrate. The said dielectric layer structure has a gradually varied dielectric constant value that is gradually regressive toward the direction of substrate.
Description
Technical field
The present invention relates to a kind of semiconductor technology, particularly relate to a kind of gate dielectric and forming method thereof.
Background technology
In recent years, fast development along with IC industry, when the direction of not stopping to dwindle toward size in the design of entire circuit element size is advanced, for the integrated level that improves element and increase its driving force, the live width design of grid must be shortened, and the thickness of gate dielectric also must dwindle thereupon.Particularly, when semiconductor technology enters epoch of deep-sub-micrometer, the thickness of gate dielectric can be reduced to the 40 Izod right sides by original hundreds of dust, and gate dielectric is very valued in the super large integrated circuit technique always.Therefore how under the little situation of the beneficial convergent of process margin (process window), to make high-quality thin gate dielectric (ultrathin gate dielectric layer), and can take into account its film layer quality, become the problem of needing solution on the technology badly.
Directly make silicon oxide layer with as gate dielectric traditionally with thermal oxidation method; and there is pin hole faults of construction such as (pin hole) in regular meeting on the structure of the silicon oxide layer of made; and then cause and directly wear tunnel electric current problems such as (direct-tunneling current), so can't be used as thin gate dielectric.Therefore, the manufacture method of existing a kind of gate dielectric is handled for carrying out a nitrogenize (nitridation), in originally purely based on the gate dielectric of silica, add silicon nitride to form so-called nitriding and oxidizing (nitrideoxide, N/O) layer, and can reduce leakage current (leakage current) and improve reliability of technology as gate dielectric with the nitriding and oxidizing layer.Yet, add that with silicon oxide layer the nitriding and oxidizing layer of the stacking-type that silicon nitride layer forms still has some problems to exist as gate dielectric.For instance, nitrogen-atoms is easy to be diffused in the nitrogen treatment process interface (interface) of silicon base and silicon oxide layer, and influences the usefulness and the stability of element.And, easily reducing resistance at the interface of silicon oxide layer and silicon nitride layer and fall into charge density, it can influence the usefulness and the stability of element equally, and then reduces the reliability of technology.
Summary of the invention
Purpose of the present invention is exactly that a kind of formation method of gate dielectric is being provided, can improve between gate dielectric and the substrate interfacial property with the interfacial property of the inner rete of gate dielectric, to improve the film layer quality of gate dielectric.
Another purpose of the present invention provides a kind of formation method of grid, can improve the stability of element and the reliability of technology.
A further object of the present invention provides a kind of gate dielectric, can improve the film layer quality of gate dielectric, promotes the reliability of technology.
Another object of the present invention provides a kind of grid, can improve the stability of element and the reliability of technology.
The present invention proposes a kind of formation method of gate dielectric, the method is for to carry out a plasma treatment process to a substrate, so that at least one plasma and this substrate reaction, to form a dielectric layer structure in substrate, wherein dielectric layer structure has the gradual change dielectric constant values (gradeddielectric constant value) that past substrate direction is successively decreased.
Described according to the preferred embodiments of the present invention, above-mentioned method is carried out a Technology for Heating Processing to this substrate after also being included in and carrying out this plasma process.
Described according to the preferred embodiments of the present invention, above-mentioned gradual change dielectric constant values is between 3.9～7.
Described according to the preferred embodiments of the present invention, above-mentioned plasma-treating technology at first carries out an oxygen plasma treatment technology, and then carries out a nitrogen plasma treatment technology.Wherein, plasma-treating technology also comprises by little to a big reacting gas (N who adjusts oxygen plasma treatment technology and nitrogen plasma treatment technology
2/ O
2) flow-rate ratio.Above-mentioned reacting gas (N
2/ O
2) flow-rate ratio is between 0～∞.
Described according to the preferred embodiments of the present invention, the operating temperature of above-mentioned plasma-treating technology is 400 ℃.
Described according to the preferred embodiments of the present invention, the concentration of the oxygen atom on the contacted surface of above-mentioned dielectric layer structure and substrate is than the concentration height of nitrogen-atoms.
Described according to the preferred embodiments of the present invention, the concentration of the nitrogen-atoms of the upper surface of above-mentioned dielectric layer structure is than the concentration height of oxygen atom.
The present invention proposes a kind of formation method of grid again, the method is for to carry out a plasma treatment process to a substrate, so that at least one plasma and this substrate reaction, to form a dielectric layer structure in substrate, wherein dielectric layer structure has the gradual change dielectric constant values that past substrate direction is successively decreased.Then, on dielectric layer structure, form a conductor layer, define conductor layer and dielectric layer structure then to form a stack structure.
Described according to the preferred embodiments of the present invention, above-mentioned method is carried out a Technology for Heating Processing to this substrate after also being included in and carrying out this plasma process.
Described according to the preferred embodiments of the present invention, above-mentioned gradual change dielectric constant values is between 3.9～7.
Described according to the preferred embodiments of the present invention, above-mentioned plasma-treating technology at first carries out an oxygen plasma treatment technology, and then carries out a nitrogen plasma treatment technology.Wherein, plasma-treating technology also comprises by little to a big reacting gas (N who adjusts oxygen plasma treatment technology and nitrogen plasma treatment technology
2/ O
2) flow-rate ratio.Above-mentioned reacting gas (N
2/ O
2) flow-rate ratio is between 0～∞.
Described according to the preferred embodiments of the present invention, the operating temperature of above-mentioned plasma-treating technology is 400 ℃.
Described according to the preferred embodiments of the present invention, the concentration of the oxygen atom on the contacted surface of above-mentioned dielectric layer structure and substrate is than the concentration height of nitrogen-atoms.
Described according to the preferred embodiments of the present invention, the concentration of the nitrogen-atoms on above-mentioned dielectric layer structure and the contacted surface of this conductor layer is than the concentration height of oxygen atom.
Described according to the preferred embodiments of the present invention, the material of above-mentioned conductor layer comprises polysilicon.
The present invention proposes a kind of gate dielectric in addition, comprises dielectric layer structure, and it has a gradual change dielectric constant values that successively decreases from top to bottom.
Described according to the preferred embodiments of the present invention, above-mentioned gradual change dielectric constant values is between 3.9～7.
Described according to the preferred embodiments of the present invention, the material on the contacted surface of above-mentioned dielectric layer structure and substrate can be a silica.
Described according to the preferred embodiments of the present invention, the material of the upper surface of above-mentioned dielectric layer structure can be a silicon nitride.
The present invention reintroduces a kind of grid, comprises substrate, dielectric layer structure and conductor layer.Wherein, dielectric layer structure is disposed in the substrate, and dielectric layer structure has the gradual change dielectric constant values that past substrate direction is successively decreased, and conductor layer is disposed on the dielectric layer structure.
Described according to the preferred embodiments of the present invention, above-mentioned gradual change dielectric constant values is between 3.9～7.
Described according to the preferred embodiments of the present invention, the material of above-mentioned conductor layer comprises polysilicon.
Described according to the preferred embodiments of the present invention, the material on the contacted surface of above-mentioned dielectric layer structure and substrate can be a silica.
Described according to the preferred embodiments of the present invention, the material on the contacted surface of above-mentioned dielectric layer structure and conductor layer can be a silicon nitride.
Utilization of the present invention is carried out a plasma treatment process forming a dielectric layer structure to substrate, and above-mentioned formed dielectric layer structure has the good interface character with substrate, and the interfacial property of the inner rete of dielectric layer structure is also preferred.Therefore, can make and improve the dielectric layer structure film layer quality, and improve reliability of technology.In addition, above-mentioned plasma-treating technology reacts at low temperatures, so can not cause the problem of surface damage to substrate.In addition, plasma-treating technology comprises that the adjustment oxygen plasma treatment technology and the flow rate of reactive gas of nitrogen plasma treatment technology compare to react, and it can be operated in same reative cell, therefore can shorten the stand-by period, and can save the technology cost.
For above and other objects of the present invention, feature and advantage can be become apparent, preferred embodiment cited below particularly, and conjunction with figs. is described in detail below.
Description of drawings
Figure 1A to Fig. 1 C is the flow process profile according to the formation method of the gate dielectric that the present invention illustrated.
Fig. 2 A to Fig. 2 B is the flow process profile according to the formation method of the grid that the present invention illustrated.
Fig. 3 is the resolution chart of electrical thickness to wafer number.
Fig. 4 is the resolution chart of leakage current to wafer number.
Fig. 5 and Fig. 6 use the resolution chart of the electric current of the N transistor npn npn of method of the present invention and P transistor npn npn to voltage.
Fig. 7 and Fig. 8 use the resolution chart of the electric capacity of the N transistor npn npn of method of the present invention and P transistor npn npn to voltage.
The simple symbol explanation
100: substrate
102: plasma-treating technology
104,104a: dielectric layer structure
106,106a: conductor layer
108: the stack structure
Embodiment
Figure 1A to Fig. 1 C is the flow process profile according to the formation method of the gate dielectric that the present invention illustrated.
At first, please refer to Figure 1A, a substrate 100 is provided, wherein substrate 100 for example is a silicon base.
Afterwards, please refer to Figure 1B, plasma-treating technology 102 is carried out in substrate 100.Above-mentioned plasma-treating technology 102 is operated at low temperatures, and the temperature of its operating environment for example is about about 400 ℃.Wherein, plasma-treating technology 102 at first carries out an oxygen plasma treatment technology, and then carries out a nitrogen plasma treatment technology.The reacting gas of oxygen plasma treatment technology is an oxygen, therefore can carry out oxidation reaction with the growth silica in substrate 100.In addition, the reacting gas of nitrogen plasma treatment technology is a nitrogen, and the reaction mechanism of nitrogen plasma treatment technology enters into silica to react for making nitrogen-atoms.
What deserve particular mention is, whole plasma-treating technology 102 is operated at low temperatures, so can not cause the problem of plasma damage film surface when carrying out plasma-treating technology to substrate 100.
In addition, above-mentioned plasma-treating technology 102 can be by little to a big reacting gas (N who adjusts oxygen plasma treatment technology and nitrogen plasma treatment technology
2/ O
2) flow-rate ratio, reacting gas (N
2/ O
2) flow-rate ratio is between 0～∞.In one embodiment, plasma-treating technology 102 can carry out oxygen plasma treatment technology and nitrogen plasma treatment technology in same reative cell (chamber), so can comparatively save the stand-by period (Queue-time) of technology.
In another embodiment, after carrying out plasma-treating technology 102, also can carry out a Technology for Heating Processing to substrate 100.Wherein, Technology for Heating Processing for example is an annealing process, and it can make the more densification of preformed rete, with its film layer quality of better raising.
Then, please refer to Fig. 1 C, after carrying out plasma-treating technology 102, can form a dielectric layer structure 104 in the substrate 100.Because, the reacting gas of plasma-treating technology 102 is nitrogen and oxygen, and in plasma-treating technology 102 reacting gas (N
2/ O
2) flow-rate ratio slowly adjust to big by little.Therefore, the concentration of the oxygen atom on dielectric layer structure 104 and substrate 100 contacted surfaces is than the concentration height of nitrogen-atoms, and the concentration of the nitrogen-atoms of the upper surface of dielectric layer structure 104 is than the concentration height of oxygen atom, thus the material of dielectric layer structure 104 by substrate 100 up in regular turn by silica, contain the more silicon oxynitride of oxygen, (that is nitrogenous more silicon oxynitride) and silicon nitride are formed to contain the less silicon oxynitride of oxygen.In other words, dielectric layer structure 104 has the gradual change dielectric constant values (graded dielectric constant value) that past substrate 100 directions are successively decreased, and the gradual change dielectric constant values is between 3.9～7.
Hold above-mentioned owing to be silica near the material of the dielectric layer structure 104 of substrate 100, its with substrate 100 between preferred interfacial characteristics is arranged, therefore can solve the boundary defect problem that has now between gate dielectric and the substrate.On the other hand, dielectric layer structure 104 can avoid producing the boundary defect problem inner as existing stacked gate dielectric layer (silicon oxide layer adds silicon nitride layer).In addition, the nitrogen content of dielectric layer structure 104 inside is higher, therefore can have the higher dielectric constant value.
In addition, in a preferred embodiment, the formation method that also can utilize gate dielectric of the present invention is to form grid, and it is described in detail as follows.
Fig. 2 A to Fig. 2 B is according to the flow process profile of the formation method of the grid that the present invention illustrated.Wherein, Fig. 2 A continues Fig. 1 C of the foregoing description carrying out, and in Fig. 2 A to Fig. 2 B, the member identical with Figure 1A to Fig. 1 C uses identical label also to omit its explanation.
Please refer to Fig. 2 A, after dielectric layer structure 104 forms, on dielectric layer structure 104, form a conductor layer 106.Wherein, the material of conductor layer 106 for example is a polysilicon, and its formation method for example is a chemical vapour deposition technique.
Then, please refer to Fig. 2 B, definition conductor layer 106 and dielectric layer structure 104 are forming a stack structure 108, and this stack structure 108 is grid.Wherein, definition conductor layer 106 for example is to carry out an etch process with the method for dielectric layer structure 104.
Wherein, the structure of above-mentioned grid comprises dielectric layer structure 104a and conductor layer 106a.Wherein, dielectric layer structure 104a is disposed in the substrate 100, and dielectric layer structure 104a has the gradual change dielectric constant values that past substrate 100 is successively decreased, and conductor layer 106a is disposed on the dielectric layer structure 104a.The material on above-mentioned dielectric layer structure 104a and substrate 100 contacted surfaces can be a silica, and the material on dielectric layer structure 104a and the contacted surface of conductor layer 106a can be a silicon nitride.
From the above, with dielectric layer structure 104a as the gate dielectric in the grid, except that can reducing equivalent oxide thickness (EOT), also can avoid the degeneration (degrdation) of gate dielectric and electricity collapse (breakdown) phenomenon takes place, and then can improve the reliability of technology.
The physical property measurement result that Fig. 3 to Fig. 8 carries out for the semiconductor element to the formation method made of using gate dielectric of the present invention.
At first, please refer to Fig. 3, it is the resolution chart of electrical thickness to wafer number (wafer No.).Tested object among the figure ( wafer number 3,4,5,6,8,9,10,11,13,14,15 and 16) carries out oxygen plasma treatment technology (plasma oxidation all earlier, and tested object can obtain three groups of different rerum natura measuring values (1.0,1.2 and 1.4nm) after oxygen plasma treatment technology PO).Then, the tested object of each group is after oxygen plasma treatment technology, carry out nitrogen plasma treatment technology (plasmanitridation again, PN), the concentration of the nitrogen that uses in [N] expression nitrogen plasma treatment technology wherein, and the nitrogen plasma concentration maximum of PN1, PN2 takes second place, and the nitrogen plasma concentration minimum of PN3.And, in each group the minimum wafer of the employed nitrogen gas concn of nitrogen plasma treatment technology after nitrogen plasma treatment technology, also comprise carry out a nitrogen treatment post growth annealing (post nitridationannealing, PNA).Wherein, wafer number 1 is the semiconductor element made from existing method, and its electrical amount of thickness measured value is 23.0.
By learning among Fig. 3, tested object employed nitrogen gas concn in nitrogen plasma treatment technology is low more, the electrical amount of thickness measured value that then records is high more, and tested object adds that after nitrogen plasma treatment technology to carry out the measured electrical amount of thickness measured value of nitrogen treatment post growth annealing higher.In addition, the electrical amount of thickness measured value of the semiconductor element made from existing method is that benchmark (be Y equal 23.0 be datum line (base line)) utilizes the electrical amount of thickness measured value result of the tested object of method of the present invention with other, compare, the electrical amount of thickness measured value of tested object that can find to utilize method of the present invention is all less than 23.0, and therefore the present invention can effectively reduce equivalent oxide thickness as can be known.
Then, please refer to Fig. 4, it is the resolution chart of leakage current to wafer number.As shown in Figure 4, tested object employed nitrogen gas concn in nitrogen plasma treatment technology is low more, the magnitude of leakage current measured value that then records is low more, and tested object adds that after nitrogen plasma treatment technology to carry out the measured magnitude of leakage current measured value of nitrogen treatment post growth annealing lower.In addition, the magnitude of leakage current measured value of the semiconductor element made from existing method is that benchmark (be Y equal 1 be datum line) utilizes the magnitude of leakage current measured value result of the tested object of method of the present invention to compare with other, the magnitude of leakage current measured value of tested object that can find to utilize method of the present invention is all greater than 1, and therefore the present invention can effectively improve the leakage phenomenon of gate dielectric as can be known.
Then, please refer to Fig. 5 and Fig. 6, it is respectively to use the resolution chart of the electric current of the N transistor npn npn of method of the present invention and P transistor npn npn to voltage.Wherein, tested object among Fig. 5 and Fig. 6 comprises with existing method, and the semiconductor element that utilizes method of the present invention (PO+PN1, PO+PN3, PO+PN3+PNA) to make, and by test result as can be known according to the current-voltage curve trend of the semiconductor element of the inventive method manufacturing, roughly the same with the current-voltage curve trend of the semiconductor element that utilizes existing method manufacturing, that is be the electrical characteristics of utilizing the semiconductor element that method of the present invention makes not second to the electrical characteristics of the semiconductor element that utilizes existing method and make.
Afterwards, please refer to Fig. 7 and Fig. 8, it is respectively to use the resolution chart of the electric capacity of the N transistor npn npn of method of the present invention and P transistor npn npn to voltage.Similarly, by Fig. 7 and Fig. 8 as can be known, capacitance-voltage curve trend according to the semiconductor element of the inventive method manufacturing, roughly the same with the capacitance-voltage curve trend of the semiconductor element that utilizes existing method manufacturing, that is be the electrical characteristics of utilizing the semiconductor element that method of the present invention makes not second to the electrical characteristics of the semiconductor element that utilizes existing method and make.
From the above, utilize method of the present invention can effectively reduce equivalent oxide thickness, and can improve the leakage current of element, can keep the electrical characteristics of element simultaneously.
In sum, the present invention has following advantage at least:
1. the present invention can effectively reduce the equivalent oxide thickness of gate dielectric, and can not influence the electrical characteristics of element.
2. plasma-treating technology of the present invention can not cause the problem of plasma damage film surface, and can carry out in same reative cell, therefore can shorten the stand-by period and save the technology cost.
3. the present invention can improve the interfacial property of gate dielectric and substrate and the interfacial property of rete inside thereof, and then can improve the reliability of technology.
Though the present invention discloses as above with preferred embodiment; yet it is not in order to limit the present invention; those skilled in the art can do a little change and retouching without departing from the spirit and scope of the present invention, thus protection scope of the present invention should with accompanying Claim the person of being defined be as the criterion.
Claims (17)
1, a kind of formation method of gate dielectric comprises:
A plasma treatment process is carried out in one substrate, so that at least one plasma and this substrate reaction, to form a dielectric layer structure in this substrate, wherein this dielectric layer structure has a gradual change dielectric constant values that successively decreases toward this substrate direction,
Wherein this plasma treatment process comprises: at first carry out an oxygen plasma treatment technology; And carry out a nitrogen plasma treatment technology again.
2, the formation method of gate dielectric as claimed in claim 1, also be included in carry out this plasma process after, a Technology for Heating Processing is carried out in this substrate.
3, the formation method of gate dielectric as claimed in claim 1, wherein this gradual change dielectric constant values is between 3.9～7.
4, the formation method of gate dielectric as claimed in claim 1, wherein this plasma treatment process also comprises:
By the little extremely big N that adjusts the reacting gas of this oxygen plasma treatment technology and this nitrogen plasma treatment technology
2And O
2Flow-rate ratio.
5, the formation method of gate dielectric as claimed in claim 4, the wherein N of this reacting gas
2And O
2Flow-rate ratio is between 0～∞.
6, the formation method of gate dielectric as claimed in claim 1, wherein the operating temperature of this plasma treatment process is 400 ℃.
7, the formation method of gate dielectric as claimed in claim 1, wherein the concentration of the oxygen atom on this dielectric layer structure and the contacted surface of this substrate is than the concentration height of nitrogen-atoms.
8, the formation method of gate dielectric as claimed in claim 1, wherein the concentration of the nitrogen-atoms of the upper surface of this dielectric layer structure is than the concentration height of oxygen atom.
9, a kind of formation method of grid comprises:
A plasma treatment process is carried out in one substrate, so that at least one plasma and this substrate reaction, to form a dielectric layer structure in this substrate, wherein this dielectric layer structure has a gradual change dielectric constant values that successively decreases toward this substrate direction;
On this dielectric layer structure, form a conductor layer; And
Define this conductor layer and this dielectric layer structure forming a stack structure,
Wherein this plasma treatment process comprises: at first carry out an oxygen plasma treatment technology; And carry out a nitrogen plasma treatment technology again.
10, the formation method of grid as claimed in claim 9, also be included in carry out this plasma process after, a Technology for Heating Processing is carried out in this substrate.
11, the formation method of grid as claimed in claim 9, wherein this gradual change dielectric constant values is between 3.9～7.
12, the formation method of grid as claimed in claim 9, wherein this plasma treatment process also comprises:
By the little extremely big N that adjusts the reacting gas of this oxygen plasma treatment technology and this nitrogen plasma treatment technology
2And O
2Flow-rate ratio.
13, the formation method of grid as claimed in claim 12, the wherein N of the reacting gas of this plasma treatment process
2And O
2Flow-rate ratio is between 0～∞.
14, the formation method of grid as claimed in claim 9, wherein the operating temperature of this plasma treatment process is 400 ℃.
15, the formation method of grid as claimed in claim 9, wherein the concentration of the oxygen atom on this dielectric layer structure and the contacted surface of this substrate is than the concentration height of nitrogen-atoms.
16, the formation method of grid as claimed in claim 9, wherein the concentration of the nitrogen-atoms on this dielectric layer structure and the contacted surface of this conductor layer is than the concentration height of oxygen atom.
17, the formation method of grid as claimed in claim 9, wherein the material of this conductor layer comprises polysilicon.
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