CN101724847A - Method for cleaning metal residue - Google Patents
Method for cleaning metal residue Download PDFInfo
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- CN101724847A CN101724847A CN200810224806A CN200810224806A CN101724847A CN 101724847 A CN101724847 A CN 101724847A CN 200810224806 A CN200810224806 A CN 200810224806A CN 200810224806 A CN200810224806 A CN 200810224806A CN 101724847 A CN101724847 A CN 101724847A
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Abstract
The invention discloses a method for cleaning a metal residue, which comprises the following steps: providing a wafer with a semiconductor structure, wherein the metal residue containing Pt remains on the semiconductor structure; and cleaning the wafer with HPM solution by a wet method and then cleaning the wafer with APM solution by the wet method so as to remove the metal residue. The method for cleaning the metal residue can fully remove the metal residue containing Pt and improves the reliability of an apparatus.
Description
Technical field
The present invention relates to technical field of manufacturing semiconductors, particularly a kind of purging method of metal residue.
Background technology
Along with super large-scale integration high integration and high performance demand are increased gradually, semiconductor technology is towards 65nm even the more technology node development of small-feature-size, and the resistance capacitance that the arithmetic speed of chip obviously is subjected to plain conductor and is caused postpones the influence of (Resistance Capacitance Delay Time, RC DelayTime).For reducing the influence of RC time-delay, can adopt metal silicide materials with low resistivity, for example titanium silicide, cobalt silicide, nickel silicide etc. are as the ohmic contact between plain conductor and the active area (Contact).
NiPtSi
xAlso be the lower metal silicide of a kind of resistivity, it has, and formation temperature is low, the characteristics of Heat stability is good, thereby is often used as the ohmic contact material of grid in 65nm and following semiconductor fabrication thereof in characteristic dimension.NiPtSi
xAdopt common silicide self-registered technology (Salicides) preparation: provide the semiconductor-based end, have source, leakage, grid at described the semiconductor-based end and be covered in medium layer on source, leakage, the grid, the contact hole that has the ohmic contact of being used to form on the described medium layer, described contact hole are respectively facing to source, leakage, grid; The metal level of deposition NiPt alloy, through behind the rapid thermal anneal process, the Si reaction in the source of described contact hole inner metal layer and lower floor, leakage, the grid generates metal silicide NiPtSi
x, carry out wet-cleaned then, remove the metal residue NiPt that is covered in unreacted metal layer on the outer medium layer of contact hole, thereby form metal silicide NiPtSi
xOhmic contact.
Above-mentioned wet clean process in conventional art, use mixing solutions (the Mixture of Sulfuric Acid Solution and Hydrogen Peroxide of sulfuric acid and hydrogen peroxide earlier, SPM) wafer is carried out pickling, use mixing solutions (the Mixture of Ammonium and HydrogenPeroxide of ammoniacal liquor and hydrogen peroxide then, APM) wafer is carried out alkali cleaning, because source, leak, the established metal silicide chemical property in surface, grid region is stable, SPM solution and APM solution all can not corrode it, thereby only remove the metal residue of unreacted metal layer on the medium layer.
Granted publication number discloses a kind of method of removing metal residue in the silicide forming process for the Chinese patent of 1326638C, this method feeds a certain amount of ozone when SPM solution and APM solution wet-cleaned, perhaps directly with the hydrogen peroxide component in ozone replacement SPM solution and the APM solution, ozone is for hydrogen peroxide, oxidisability is stronger, be difficult for decomposing and cost lower, can improve the effect of wet-cleaned and reduce production costs.
Yet problem is that along with feature sizes of semiconductor devices develops into 65nm and following, the ohmic contact material also more adopts NiPtSi
xSubstitute titanium silicide, cobalt silicide, traditional wet clean process is removed and is formed metal silicide NiPtSi
xDuring metal residue NiPt in the process, actual effect is unsatisfactory, and the Pt that has part can not remove fully, remains on medium layer surface, contact hole sidewall or the grid region side wall, and the reliability of device is produced serious harm.
Same, in other technological processs of semi-conductor manufacturing, also might there be the metal residue that contains Pt, and the method that above-mentioned traditional SPM solution and the combination of APM solution are cleaned can not be removed the Pt in the metal residue fully, will produce detrimentally affect to the electric property of device.
Summary of the invention
The problem that the present invention solves provides a kind of purging method of metal residue, can remove metal remained Pt more fully, improves the reliability of device.
For addressing the above problem, the invention provides a kind of removal method of metal residue, comprising:
Wafer with semiconductor structure is provided, has the metal residue that contains Pt on the described semiconductor structure;
(Mixture of Hydrogen Chlorine andHydrogen Peroxide, HPM) the described wafer of wet-cleaned adopts the described wafer of APM solution wet-cleaned, thereby removes described metal residue the mixing solutions of employing hydrochloric acid and hydrogen peroxide then earlier.
In addition, before adopting the described wafer of HPM solution wet-cleaned, can also comprise: adopt the described wafer of a SPM solution wet-cleaned.
In addition, before adopting the described wafer of APM solution wet-cleaned, can also comprise: adopt the described wafer of the 2nd SPM solution wet-cleaned.
HCl and H in the described HPM solution
2O
2The volume by volume concentration value can be 2 to 4.
H in a described SPM or the 2nd SPM solution
2SO
4And H
2O
2The volume by volume concentration value can be 3 to 5.
Optionally, the time of described employing HPM solution wet-cleaned wafer can be 90 seconds to 630 seconds, and the temperature of described HPM solution can be 40 ℃ to 70 ℃.
Optionally, the time of described employing the one SPM solution wet-cleaned wafer can be 360 seconds, and the temperature of a described SPM solution can be 80 ℃ to 99 ℃.
Optionally, the time of described employing the 2nd SPM solution wet-cleaned wafer is 180 seconds, and the temperature of described the 2nd SPM solution can be 80 ℃ to 99 ℃.
Optionally, the time of described employing APM solution wet-cleaned wafer is 300 seconds, and described APM solution temperature is 30 ℃ to 35 ℃.
Preferably, described wet-cleaned adopts the spraying cleaning technique.
Compared with prior art, technique scheme has the following advantages:
The purging method that adopts HPM solution to replace SPM solution in the traditional method can obtain better cleaning performance, this is because the chemical property of metal Pt is more stable than metal Ni, SPM solution almost can not react with Pt, thereby can't well remove metal residue, yet the reaction that HPM solution can take place with metal Pt contains Pt soluble compound H and the metal Pt in the metal residue changed into
2PtCl
6After washed with de-ionized water, can remove then from substrate surface, and the metal Ni of HPM solution in also can the flush away metal residue cleans with APM solution and removes residual pollutent and the HPM solution that neutralizes residual, thereby remove the metal residue that contains Pt fully.
In addition, adopt before the HPM solution clean wafers and all adopt SPM solution to clean afterwards, can fully remove metal residue, because at first adopt the metal Ni in the SPM solution removal metal residue, at this moment, having part is not removed with the metal Ni of metal Pt chemistry or physical bond, then adopt the metal Pt in the HPM solution removal metal residue, adopt the 2nd SPM solution further to remove the residual part metals particle of wafer surface then, for example, a SPM solution is failed flush away and metal Ni metal Pt chemistry or physical bond.
Description of drawings
Shown in accompanying drawing, above-mentioned and other purpose, feature and advantage of the present invention will be more clear.Reference numeral identical in whole accompanying drawings is indicated identical part.Painstakingly do not draw accompanying drawing, focus on illustrating purport of the present invention by physical size equal proportion convergent-divergent.
Fig. 1 is the schema of the removal method of metal residue among the embodiment one;
Fig. 2 to Fig. 5 is the synoptic diagram of the making processes of metal silicide among the embodiment one;
Fig. 6 is the optical photograph of wafer after the wet-cleaned among the embodiment one;
Fig. 7 is the schema of the removal method of metal residue among the embodiment two;
Fig. 8 is the schema of the removal method of metal residue among the embodiment three;
Fig. 9 is the optical photograph of the wafer after the wet-cleaned among the embodiment three.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, the specific embodiment of the present invention is described in detail below in conjunction with accompanying drawing.
A lot of details have been set forth in the following description so that fully understand the present invention, but the present invention can also adopt other to be different from alternate manner described here and implement, those skilled in the art can do similar popularization under the situation of intension of the present invention, so the present invention is not subjected to the restriction of following public specific embodiment.
Secondly, the present invention is described in detail in conjunction with synoptic diagram, when the embodiment of the invention is described in detail in detail; for ease of explanation; the sectional view of expression device architecture can be disobeyed general ratio and be done local the amplification, and described synoptic diagram is example, and it should not limit the scope of protection of the invention at this.The three-dimensional space size that in actual fabrication, should comprise in addition, length, width and the degree of depth.
In the ic manufacturing process, in substrate, form earlier semiconducter device, then on semiconducter device, form the multiple layer metal lead, be used for a plurality of semiconducter device in the substrate are electrically connected; Be electrically connected by metal closures between between the multiple layer metal lead and the source of the first layer plain conductor and semiconducter device, leakage, the grid.Has ohmic contact between the source of described metal closures and semiconducter device, leakage, the grid, this ohmic contact adopts the metal silicide materials of low resistivity to make, with the series resistance between reduction metal closures and the semiconducter device, and prevent that the metal in the metal closures from spreading to lower floor.
Ohmic contact adopts silicide self-registered technology (Salicides) preparation usually: the semiconductor-based end is provided, have source, leakage, grid region at described the semiconductor-based end and be covered in medium layer on source, leakage, the grid region, the contact hole that has the ohmic contact of being used to form on the described medium layer, described contact hole are respectively facing to source, leakage, grid region; Depositing metal layers, through behind the rapid thermal anneal process, Si reaction in the metal level in the described contact hole and the source of lower floor, leakage, the grid region generates metal silicide, carry out wet-cleaned then, removal is covered in the metal residue of unreacted metal layer on the outer medium layer of contact hole, thereby forms the ohmic contact of being made up of metal silicide.
In characteristic dimension is in the semiconductor fabrication of 90nm, metal silicide is mainly cobalt silicide, the corresponding metal residue is a cobalt, traditional wet clean process, earlier carry out pickling, carry out alkali cleaning with APM solution then, owing to source, leakage, the established cobalt silicide chemical property in surface, grid region are stablized with SPM solution, SPM solution and APM solution all can not corrode it, thereby only remove unreacted metal residue cobalt on the medium layer.
When semiconductor fabrication develops into characteristic dimension is 65nm and when following, and the ohmic contact material also more adopts NiPtSi
xSubstitute titanium silicide, cobalt silicide, traditional wet clean process is removed and is formed metal silicide NiPtSi
xDuring metal residue NiPt in the process, actual effect is unsatisfactory, and the Pt that has part can not remove fully, remains on medium layer surface, contact hole sidewall or the grid region side wall, and the reliability of device is produced serious harm.
The contriver thinks that the reason that produces the problems referred to above is the sulfuric acid (H in the SPM solution
2SO
4) can with Ni among metal residue NiPt reaction, converts it into soluble substance and remove, but the Pt chemical property among the metal residue NiPt is more stable than Ni from substrate, general condition is difficult for down and sulfuric acid reaction, and remains in the substrate.
Therefore, embodiments of the invention provide a kind of removal method of metal residue, comprising: the wafer with semiconductor structure is provided, has the metal residue that contains Pt on the described semiconductor structure; Adopt the described wafer of HPM solution wet-cleaned earlier, adopt the described wafer of APM solution wet-cleaned then, thereby remove described metal residue.
In addition, before adopting the described wafer of HPM solution wet-cleaned, can also comprise: adopt the described wafer of a SPM solution wet-cleaned.
In addition, before adopting the described wafer of APM solution wet-cleaned, can also comprise: adopt the described wafer of the 2nd SPM solution wet-cleaned.
HCl and H in the described HPM solution
2O
2The volume by volume concentration value can be 2 to 4.
H in a described SPM or the 2nd SPM solution
2SO
4And H
2O
2The volume by volume concentration value can be 3 to 5.
Optionally, the time of described employing HPM solution wet-cleaned wafer can be 90 seconds to 630 seconds, and the temperature of described HPM solution can be 40 ℃ to 70 ℃.
Optionally, the time of described employing the one SPM solution wet-cleaned wafer can be 360 seconds, and the temperature of a described SPM solution can be 80 ℃ to 99 ℃.
Optionally, the time of described employing the 2nd SPM solution wet-cleaned wafer is 180 seconds, and the temperature of described the 2nd SPM solution can be 80 ℃ to 99 ℃.
Optionally, the time of described employing APM solution wet-cleaned wafer is 300 seconds, and described APM solution temperature is 30 ℃ to 35 ℃.
Preferably, described wet-cleaned adopts the spraying cleaning technique.
Embodiment one
Making processes with metal silicide is the preferred embodiment that background describes the removal method of described metal residue in detail.Fig. 1 is the schema of the removal method of described metal residue.
Step S1: the wafer with semiconductor structure is provided, has the metal residue that contains Pt on the described semiconductor structure.
Concrete, as shown in Figure 2, providing substrate 100, this substrate 100 can be the wafer of silicon single crystal.Has semiconducter device in the substrate 100, for example described semiconducter device is metal-oxide semiconductor (MOS) (MOS) transistor, two MOS transistors only are shown among Fig. 2, and two MOS transistors have shallow channel isolation area (STI) 109, so that different semiconducter device isolated insulations.
Described MOS (metal-oxide-semiconductor) transistor comprises source electrode 102, drain electrode 104 and grid 106, has grid oxic horizon 108 between substrate 100 and grid 106.Also has grid curb wall layer 107 at described grid 106 sidewalls.
As shown in Figure 3, form metal level 110 on described MOS transistor, the pasc reaction that is used for wafer forms metal silicide, as the ohmic contact between the metal carbonyl conducting layer of MOS transistor and follow-up formation.Metal level 110 is the NiPt alloy in the present embodiment, adopt physical vaporous deposition (PhysicalChemical Deposition, PVD) preparation, described physical vaporous deposition can be magnetron sputtering technique, metal level 110 covers source electrode 102, drain electrode 104 and the grid 106 of described MOS transistor, and also described grid curb wall layer 107, shallow channel isolation area 109 are covered, the thickness of this metal level 110 is about 30nm to 500nm.
As shown in Figure 4, place annealing device to carry out rapid thermal anneal process the wafer that has MOS transistor in the above-mentioned substrate 100, make the pasc reaction in source electrode 102, drain electrode 104 and the grid 106 of metal level 110 below it, thereby form metal silicide 112, for example, metal level 110 is the NiPt alloy, and NiPt alloy and pasc reaction form and generate metal silicide NiPtSi
xAnd grid curb wall layer 107, shallow channel isolation area 109 are made up of dielectric materials such as silicon oxide, silicon oxynitride, silicon nitrides, metal level 110 does not react with described dielectric material, after forming metal silicide 112, covering the metal level 110a on grid curb wall layer 107, the shallow channel isolation area 109 and all remain in the surface of described MOS transistor with source electrode 102, drain electrode 104 and the remaining metal level 110b of grid 106 reaction, is metal residue 111 at this nominal.
As shown in Figure 5, remove metal residue 111 (see figure 4)s, thereby the metal silicide 112 that will form before this exposes, so that the metal silicide 112 and the metal carbonyl conducting layer of backend process are electrically connected.
The step of described removal metal residue 111 is carried out in the washing unit in spraying, during cleaning, is ejected into the wafer that places sealed chamber in after the scavenging solution that is used for wet-cleaned is atomized, and wafer is placed in the interior rotatable wafer rack of chamber.The advantage of spraying washing unit is can sustainable supply deployed in advance scavenging solution and is ejected into wafer, when the small droplets of the scavenging solution that ejects arrives wafer surface with very high flow attack, to produce a physics momentum to wafer surface, can effectively strengthen the effect of cleaning, in addition, scavenging solution sprays with atomizing state, can rationally control the consumption of scavenging solution, help saving cost, improve cleaning efficiency.
Detailed process as shown in Figure 1, with reference to step S2: adopt the wafer that has MOS transistor in the described substrate 100 of HPM solution wet-cleaned.Described HPM solution is hydrochloric acid (HCl) and hydrogen peroxide (H
2O
2) mixing solutions, its volume by volume concentration is HCl: H
2O
2=(2-4): 1, during cleaning, to be injected into wafer surface behind the pre-configured HPM solution atomization, wherein the temperature of HPM solution is controlled at 40 ℃ to 70 ℃ scope, for example 45 ℃, 50 ℃, 60 ℃, in this temperature range, HPM solution can be fully and alloy NiPt reaction, is translated into soluble compound; The time of adopting HPM solution to clean is 90 seconds to 630 seconds, for example 120 seconds, 180 seconds, 320 seconds, preferred scavenging period is 180 seconds, scavenging period is too short will be insufficient with the reaction of metal residue, long other medium of oxides layers, for example grid curb wall layer 107, the shallow channel isolation area 109 etc. of then may damaging of scavenging period; Washed with de-ionized water liquid is injected into wafer surface then, thereby with the compound flush away of described solubility.
Preferably, HPM liquor capacity specific concentration is HCl: H
2O
2=3.17: 1,50 ℃ of the temperature of HPM solution, scavenging period is under 180 seconds the condition, HPM solution has higher etching selection ratio to the grid curb wall layer 107 on the wafer, shallow channel isolation area 109, not only can fully clean and remove metal residue 111, and not damage other structures such as grid curb wall layer 107, shallow channel isolation area 109.
Then with reference to step S3: adopt the described wafer of APM solution wet-cleaned, with the HPM solution of removing residual pollutent and neutralizing residual.Described APM solution is ammoniacal liquor (NH
4OH) and hydrogen peroxide (H
2O
2) mixing solutions, its volume ratio is NH
4OH: H
2O
2: H
2O=1: 2: 50.This step S3 scavenging period is 300 seconds, during cleaning, will be injected into substrate 100 surfaces behind the pre-configured APM solution atomization, and the temperature of APM solution is controlled at 30 ℃ to 35 ℃ scope, then adopts washed with de-ionized water.
Finish and clean and clean after the detection of back, the sealed chamber of cleaning system feeds the heated nitrogen washing, and the rotation wafer makes its drying.
Removal method with respect to traditional metal residue, promptly adopt SPM solution to adopt the method for APM solution cleaning more earlier, the above-mentioned purging method that adopts HPM solution to replace SPM solution in the traditional method earlier can obtain better cleaning performance, this is because the chemical property of metal Pt is more stable than metal Ni, SPM solution almost can not react with Pt, thereby can't well remove metal residue 111, yet HPM solution can take place with metal Pt as the reaction of following formula (1), contains Pt soluble compound H thereby the metal Pt in the metal residue 111 changed into
2PtCl
6, remove with washed with de-ionized water then.
Pt+2HCl+2Cl
2＝H
2PtCl
6 (1)
Fig. 6 is the optical photograph of the wafer after cleaning, wherein, right figure is the wafer that adopts traditional purging method to clean, left side figure is the wafer that adopts the purging method described in the present embodiment to clean, the black round dot represents to remain in the metal residual composition granule on the wafer surface, as seen, the removal method of the metal residue described in the present embodiment is compared traditional method and can better be removed metal residue.
In addition, before adopting HPM solution clean wafers, can also clean with SPM solution earlier, can obtain better cleaning performance, specifically in following examples, describe in detail.
Embodiment two
Fig. 7 is the schema of the removal method of the described metal residue of present embodiment.
With reference to steps A 1: the wafer with semiconductor structure is provided, has the metal residue that contains Pt on the described semiconductor structure.This steps A 1 is identical with the step S1 of embodiment one, specifically can not repeat them here with reference to Fig. 2 to Fig. 5.
With reference to steps A 2: adopt the wafer that has MOS transistor in the described substrate 100 of SPM solution wet-cleaned, to remove the metal Ni in the metal residue 111.Described SPM solution is sulfuric acid (H
2SO
4) and hydrogen peroxide (H
2O
2) mixing solutions, its volume by volume concentration is H
2SO
4: H
2O
2=(3-5): 1, during cleaning, to be injected into wafer surface behind the pre-configured SPM solution atomization, the temperature of described SPM solution is controlled at 80 ℃ to 99 ℃ scope, for example, 85 ℃, 90 ℃, 95 ℃, in this temperature range, SPM solution can be fully and metal Ni reaction, be translated into the soluble compound that contains Ni, preferred, described SPM solution temperature is 95 ℃, temperature is lower than this, the chemical reactivity of SPM solution is lower, be unfavorable for removing metal residue, and temperature is higher than this, to be unfavorable for forming spraying near the boiling point of SPM solution; The time of adopting SPM solution to clean is 360 seconds, sprays washed with de-ionized water liquid then to wafer surface, thereby the compound of the solubility of the above-mentioned Ni of containing is removed from wafer surface.
Then with reference to steps A 3: adopt the wafer that has MOS transistor in the described substrate 100 of HPM solution wet-cleaned, to remove the metal Pt in the metal residue 111.This steps A 3 is similar with the step S2 of embodiment one, and described HPM solution is the mixing solutions of hydrochloric acid (HCl) and hydrogen peroxide, and its volume by volume concentration is HCl: H
2O
2=(2-4): 1, during cleaning, substrate 100 surfaces will be injected into behind the pre-configured HPM solution atomization, the temperature of HPM solution is controlled at 40 ℃ to 70 ℃ scope, for example 45 ℃, 50 ℃, 60 ℃, in this temperature range, HPM solution can be fully and metal Pt reaction, is translated into the soluble compound that contains Pt; The time of adopting HPM solution to clean is 90 seconds to 630 seconds, and for example 120 seconds, 180 seconds, 320 seconds, washed with de-ionized water liquid was injected into wafer surface then, thereby the compound of the solubility of the above-mentioned Pt of containing is removed from wafer surface.
Then with reference to steps A 4: adopt the described wafer of APM solution wet-cleaned, with SPM solution or the HPM solution of removing residual pollutent and neutralizing residual.Described APM solution is ammoniacal liquor (NH
4OH) and hydrogen peroxide (H
2O
2) mixing solutions, its volume ratio is NH
4OH: H
2O
2: H
2O=1: 2: 50.This step S3 scavenging period is 300 seconds, during cleaning, will be injected into substrate 100 surfaces behind the pre-configured APM solution atomization, and wherein the temperature of APM solution is controlled at 30 ℃ to 35 ℃ scope, then adopts washed with de-ionized water.
After finishing cleaning and cleaning the back detection, the sealed chamber of cleaning system feeds heated nitrogen and washs, and the rotation wafer makes its drying.
The contriver discovers, during wet-cleaned, the SPM solution that adopts is obvious to the Ni removal effect in the metal residue 111 earlier, and can not remove the more stable metal Pt of chemical property, after SPM solution cleans, adopt HPM solution clean wafers can remove not metal Pt with the SPM solution reaction again, reach better cleaning performance.
In addition, also can after adopting HPM solution clean wafers, adopt SPM solution to clean, then clean with APM solution again, also can realize same cleaning performance.
In addition, also can and all adopt SPM solution to clean afterwards before adopting the cleaning of HPM solution, specifically in following examples, describe in detail.
Embodiment three
Fig. 8 is the schema of the removal method of the described metal residue of present embodiment.
With reference to step B1: the wafer with semiconductor structure is provided, has the metal residue that contains Pt on the described semiconductor structure.This step B1 is identical with the step S1 of embodiment one, specifically can not repeat them here with reference to Fig. 2 to Fig. 5.
With reference to step B2: adopt a SPM solution wet-cleaned substrate 100, to remove the metal Ni in the metal residue 111.A described SPM solution is sulfuric acid (H
2SO
4) and hydrogen peroxide (H
2O
2) mixing solutions, its volume by volume concentration is H
2SO
4: H
2O
2=(3-5): 1, during cleaning, to be injected into wafer surface behind the pre-configured SPM solution atomization, the temperature of the one SPM solution is controlled at 80 ℃ to 99 ℃ scope, for example, 85 ℃, 90 ℃, 95 ℃, in this temperature range, the one SPM solution can be fully and metal Ni reaction, be translated into the soluble compound that contains Ni, preferred, a SPM solution temperature is 95 ℃, temperature is lower than this, the chemical reactivity of the one SPM solution is lower, be unfavorable for removing metal residue, and temperature is higher than this, to be unfavorable for forming spraying near the boiling point of a SPM solution; The time of adopting a SPM solution to clean is 360 seconds, sprays washed with de-ionized water liquid then to wafer surface, thereby the above-mentioned compound that contains the solubility of Ni is removed.
Then with reference to step B3: adopt the described wafer of HPM solution wet-cleaned, to remove the metal Pt in the metal residue 111.The step S2 of this step B3 and embodiment one is similar, and described HPM solution is the mixing solutions of hydrochloric acid (HCl) and hydrogen peroxide, and its volume by volume concentration is HCl: H
2O
2=(2-4): 1, during cleaning, to be injected into wafer surface behind the pre-configured HPM solution atomization, the temperature of described HPM solution is controlled at 40 ℃ to 70 ℃ scope, for example 45 ℃, 50 ℃, 60 ℃, in this temperature range, HPM solution can be fully and metal Pt reaction, is translated into the soluble compound that contains Pt, and is preferred, the temperature of HPM solution is 50 ℃, temperature is higher than this, may cause the volatilization of HCl, and temperature is lower than this, the chemical reactivity of HPM solution is lower, is unfavorable for removing metal residue; The time of adopting HPM solution to clean is 90 seconds to 630 seconds, and for example 120 seconds, 180 seconds, 320 seconds, washed with de-ionized water liquid was injected into wafer surface then, thereby the above-mentioned compound that contains the solubility of Pt is removed.
Preferably, HPM liquor capacity specific concentration is HCl: H
2O
2=3.17: 1,50 ℃ of HPM solution temperatures, scavenging period are under 180 seconds the condition, HPM solution has higher etching selection ratio to the grid curb wall layer 107 on the wafer, shallow channel isolation area 109, and it is very fast with the metal residue speed of reaction, not only can fully clean and remove metal residue 111, and not damage other structures such as grid curb wall layer 107, shallow channel isolation area 109.
Then with reference to step B4: adopt the described wafer of the 2nd SPM solution wet-cleaned, thereby further remove the part metals particle of substrate 100 remained on surface.Wherein, a SPM solution is similarly sulfuric acid (H described in described the 2nd SPM solution and the step S2
2SO
4) and hydrogen peroxide (H
2O
2) mixing solutions, its volume by volume concentration also is H
2SO
4: H
2O
2=(3-5): 1 (" first " here only represented the different of cleaning sequence with " second "), this step S4 scavenging period is 180 seconds, and during cleaning, the temperature of the 2nd SPM solution also is controlled at 80 ℃ to 99 ℃ scope, for example, 85 ℃, 90 ℃, 95 ℃; Then adopt cleaning the 2nd SPM solution of deionized water and the soluble compound that metal residue 111 reactions generate.
At last with reference to step B5: adopt the described wafer of APM solution wet-cleaned, with SPM solution or the HPM solution of removing residual pollutent and neutralizing residual.Described APM solution is ammoniacal liquor (NH
4OH) and hydrogen peroxide (H
2O
2) mixing solutions, its volume ratio is NH
4OH: H
2O
2: H
2O=1: 2: 50.This step S5 scavenging period is 300 seconds, during cleaning, will be injected into substrate 100 surfaces behind the pre-configured APM solution atomization, and wherein the temperature of APM solution is controlled at 30 ℃ to 35 ℃ scope, then adopts washed with de-ionized water.Step S3 among this step B5 and the embodiment one is similar, does not repeat them here.
After finishing cleaning and cleaning the back detection, the sealed chamber of cleaning system feeds heated nitrogen and washs, and the rotation wafer makes its drying.
Adopt in the present embodiment HPM solution clean before and all adopt SPM solution to clean afterwards, can fully remove metal residue, because at first adopt the metal Ni in the SPM solution removal metal residue 111, at this moment, having part is not removed with the metal Ni of metal Pt chemistry or physical bond, then adopt the metal Pt in the HPM solution removal metal residue 111, adopt the 2nd SPM solution further to remove the part metals particle of substrate 100 remained on surface then, for example, a SPM solution is failed flush away and metal Ni metal Pt chemistry or physical bond.
Fig. 9 is the optical photograph of the wafer after cleaning, wherein, right figure is the wafer that adopts traditional purging method to clean, left side figure is the wafer that adopts the purging method described in the present embodiment to clean, the black round dot represents to remain in the metal residual composition granule on the wafer surface, as seen, the removal method of the metal residue described in the present embodiment is compared traditional method can better remove metal residue, does not almost have the particle of metal residue on the wafer.
Wet-cleaned all adopts the spraying cleaning technique among the last embodiment, also can adopt other wet-cleaned technology in addition, and for example, million cleanings (Megasonics), overflow cleaning etc. are all within protection scope of the present invention.
The above only is preferred embodiment of the present invention, is not the present invention is done any pro forma restriction.
Though the present invention discloses as above with preferred embodiment, yet be not in order to limit the present invention.Any those of ordinary skill in the art, do not breaking away under the technical solution of the present invention scope situation, all can utilize the method and the technology contents of above-mentioned announcement that technical solution of the present invention is made many possible changes and modification, or be revised as the equivalent embodiment of equivalent variations.Therefore, every content that does not break away from technical solution of the present invention, all still belongs in the scope of technical solution of the present invention protection any simple modification, equivalent variations and modification that above embodiment did according to technical spirit of the present invention.
Claims (10)
1. the removal method of a metal residue is characterized in that, comprising:
Wafer with semiconductor structure is provided, has the metal residue that contains Pt on the described semiconductor structure;
Adopt the described wafer of HPM solution wet-cleaned earlier, adopt the described wafer of APM solution wet-cleaned then, thereby remove described metal residue.
2. the removal method of metal residue according to claim 1 is characterized in that, also comprises before adopting the described wafer of HPM solution wet-cleaned: adopt the described wafer of a SPM solution wet-cleaned.
3. the removal method of metal residue according to claim 1 and 2 is characterized in that, also comprises before adopting the described wafer of APM solution wet-cleaned: adopt the described wafer of the 2nd SPM solution wet-cleaned.
4. the removal method of metal residue according to claim 3 is characterized in that, HCl and H in the described HPM solution
2O
2The volume by volume concentration value be 2 to 4.
5. the removal method of metal residue according to claim 3 is characterized in that, H in a described SPM or the 2nd SPM solution
2SO
4And H
2O
2The volume by volume concentration value be 3 to 5.
6. the removal method of metal residue according to claim 3 is characterized in that, the time of described employing HPM solution wet-cleaned wafer is 90 seconds to 630 seconds, and the temperature of described HPM solution is 40 ℃ to 70 ℃.
7. the removal method of metal residue according to claim 3 is characterized in that, the time of described employing the one SPM solution wet-cleaned wafer is 360 seconds, and the temperature of a described SPM solution is 80 ℃ to 99 ℃.
8. the removal method of metal residue according to claim 3 is characterized in that, the time of described employing the 2nd SPM solution wet-cleaned wafer is 180 seconds, and the temperature of described the 2nd SPM solution is 80 ℃ to 99 ℃.
9. according to the removal method of the described metal residue of claim 3, it is characterized in that the described employing APM solution wet-cleaned wafer time is 300 seconds, described APM solution temperature is 30 ℃ to 35 ℃.
10. the removal method of metal residue according to claim 1 and 2 is characterized in that, described wet-cleaned adopts the spraying cleaning technique.
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| CN102290325A (en) * | 2010-06-21 | 2011-12-21 | 无锡华润上华半导体有限公司 | Method for cleaning metallic silicides |
| CN102420132A (en) * | 2011-05-26 | 2012-04-18 | 上海华力微电子有限公司 | Method for removing NiPt metallic silicide |
| WO2012155289A1 (en) * | 2011-05-16 | 2012-11-22 | 北京通美晶体技术有限公司 | Iii-v group compound semiconductor wafer and cleaning method thereof |
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