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USOO5681397A
United States Patent [19] [11] Patent Number: 5,681,397
Li ['45] Date of Patent: Oct. 28, 1997

[54] METHODS FOR HIGH TEMPERATURE Handbook of Semiconductor Wafer Cleaning Technology
WATER RINSING AND DRYING OF SILICON Edited by Werner Kern, Noyes Publications, 1993, pp.
WAFERS AFTER BEING CLEANED IN
HYDROFLUORIC ACID 134-135.

[75] Inventor: Li Li, Meridian, Id.
Primary Examiner-Robert J. Warden
[73] Assignee: Micron Technology, Inc., Boise, Id. Assistant Examiner—Alexander Marko?’
Attorney Agent, or Firm—-Workman, Nydegger and Seeley
[21] Appl. No.: 527,339
[57] ABSTRACT
[22] Filed: Sep. 12, 1995
[51] Int. Cl.6 ................................................... .. coac 23/00 Methods are disclosed for rinsing and drying of a silicon
[52] Us. 01. ................................... .. 134/2; 134/3; 134/26; wafer. The methods involve cleaning the silicon wafer with
134/23 hydro?uoric acid, immersing a silicon wafer in either boil
[58] Field of Search ............................... .. 134/2, 3, 26, 2s v
ing deionized water or a boiling hydrochloric acid solution,
[56] References Cited and then drawing the silicon wafer to dry from the boiling
U.S. PATENT DOCUMENTS deionized Water or the boiling aqueous hydrochloric acid
solution. The aqueous hydrochloric acid solution preferably
4,716,050 12/1987 Greenetal. ............................ .. 427/99
has a pH value of about 2.5. Oxidation of the surfaces of a
OTHER PUBLICATIONS silicon Wafer is minimized by immersing the silicon wafer in
Nayami et a1, Removal of Metallic contaminants and Native either boiling water or a boiling aqueous hydrochloric acid
oxide Prom silicon wafer surface by pure water containing solution thereby yielding a Wafer having surfaces which are
a little dissolved Oxygen Mat. Res. Soc. Symp. Proc. vol. oxide free. A silicon wafer boiled in an aqueous hydrochloric
386, pp. 69-74, Apr. 1995. acid solution experiences minimal surface toughening and
Li et a1. Surface Passivation and Microroughness of (100)
Silicon Etched in Aqueous Hydrogen Halide (HF, HCI H8, has relatively smooth surfaces.
H1) Solutions, 1. Appl. Phys, 77(3), 1 Feb. 1995,
1323-1325. 12 Claims, 5 Drawing Sheets

15

mi 9 El 9 Q
65: 1:1 B0|L|NGHCl(aq){pH=2.5)
CONTACT 60_ O x BOILING WATER
All(§;)LE - 0 HOT WATER (80°C)

10 15 20
TIME (min.)

US. EE Q 52 65. El BOILING HCl(aq)(pH=2.397 m. 1997 Sheet 1 of5 5.681. Patent 0a. O 0 HOT WATER (80°C) TIME (min. 1 .) FIG.5) CONTACT so: A BOILINGWATER AN{G)LE 0 . 28.

‘ | l 2300 2200 2100 2000 WAVENUMBER (cm'1) FIG.smx 0. _ BUlUNG. Patent 0a. 28.397 0. ‘ ABSORBANCE 0.02 .US.5 0.03 .04 l I I I I _ .01 _ "‘ B0|L|NG -REF - 0'00 \ ‘ ~. 2 . pH 2.681. 1997 Sheet 2 of 5 5. ? .

04 — ABS 0 RBA N C E “'01 REF ' 0.US. 3 . 30°02 2000 2200 2100 2000 WAVENUMBER (cm-1) FIG.397 0. 28. 1997 Sheet 3 of 5 5.00 .681. Patent 000.

40 . 4B 200 300 FIG. 1997 Sheet 4 of 5 5.397 300 FIG. 4A 200 300 FIG.US. 28.681. Patent Oct.

28.397 ABSORBANCE 2160 2100 2040 WAVENUMBER (cm-0 FIG.681. 5 . Patent Oct.US. 1997 Sheet 5 of 5 5.

A silicon wafer boiled in an aqueous hydro of the capillary action of heated water when hot water 45 chloric acid solution having a pH level of about 2. hot water rinsing also wafer. The surfaces of HF-treated wafers are 50 silicon wafer has been cleaned in an aqueous hydro?uoric easily attacked by oxidants such as 0H“ radicals during acid solution.5 has no immersed wafers are slowly pulled to air at a controlled rate. however. drying a silicon wafer without oxidizing the surfaces of the Hot deionized water having a temperature of about 85° C. the methods involve treating a silicon wafer with boiling water 1. HF treatment removes 25 by immersing a silicon wafer in either boiling water or a thermal and native oxides and is therefore an essential boiling aqueous hydrochloric acid solution thereby yielding processing step of device fabrication and in particular also a a wafer having surfaces which are oxide free. aqueous hydrochloric acid have a rrns roughness of less than such as the TRE'BOR HydrodryTM technique. boiling water after the wafer has been exposed to hydrof The methods of the present invention comprise the steps luoric acid in order to provide an oxide free and smooth of immersing a silicon wafer in a boiling hydrochloric acid silicon surface.2 nm. several commercial invention will become more fully apparent from the follow ized drying techniques are on the market now which use ing description and appended claims. 55 silicon wafer. The roughening effect of the boiling water on 20 decrease to the deep sub-micron region. HF treated by the methods of the present invention has surfaces treatment of silicon wafers by HF-last cleaning techniques with no more oxides than after the silicon wafer has been has been the main approach over the last few years for 30 cleaned in an aqueous hydro?uoric acid solution. take advantage about 0. 5. the practice of the invention as set forth hereinafter. is very susceptible to particle contamination. remove the oxygen from the water and prevent the reentry however. more microroughness on the surfaces of the silicon wafer HF-treated silicon surfaces are found to be almost com after the silicon wafer has been immersed in the boiling pletely hydrogen terminated. it also roughens and smooth surfaces. however. silicon wafers are continually being developed and opti Immersing a silicon wafer in boiling water suppresses mized to meet the stringent demands for wafers having clean reoxidation of the silicon surfaces. solution and then drawing the silicon wafer from the boiling 15 2. hydrochloric acid solution having a pH of about 2. Wafer drying techniques play a critical role in reducing the The surface roughening due to the etching reaction of particle attraction to the hydrophobic silicon surface. The boiling temperature water rinsing and drying of silicon wafers after water is preferably spiked with su?icient hydrochloric acid being cleaned with hydro?uoric acid. increases the chemical solubilities and reduces the boundary It is also an object of the present invention to provide layer effect on the wafer surface. the silicon wafers ciently oxide free that a droplet of deionized water on one of are normally proceeded by particle and organic removal the surfaces of a silicon wafer has a contact angle of about steps. HF-last processing. After the wafers have been aqueous hydrochloric acid solution and drawn from the treated with hydro?uoric acid. As the device features continuously the surfaces.5. recited and other advantages and objects of the invention are . The reoxidation is accelerated in the present invention is to provide methods for rinsing and hot DI water. Prior to oxide removal ods of the present invention yield wafers which are suffi with HF or the HF-last pre-diffusion clean. More particularly.5. the wafers are rinsed in boiling aqueous hydrochloric acid solution than after the deionized (DI) water. Prior art wafer drying techniques. IPA drying and the TREBOR tion such that the surfaces of a silicon wafer boiled in HydrodryTM technique. the 10 (HCl) to yield an aqueous hydrochloric acid solution having methods involve treating a silicon wafer with HCl added to a pH value of about 2. 70°. A wafer basic component of all kinds of cleaning procedures.681. More particularly. of the oxygen. thereby decreasing the methods for rinsing and drying a silicon wafer with minimal rinse time. Rinsing in hot water provides enhanced etching reoxidation and roughening of the surfaces of the silicon with an anisotropic etch rate.397 1 2 METHODS FOR HIGH TEMPERATURE SUMMARY AND OBJECI‘S OF THE WATER RINSING AND DRYING OF SHJICON INVENTION WAFERS AFTER BEING CLEANED IN The present invention is directed to methods for high HYDROFLUORIC ACID temperature water rinsing and drying of a silicon wafer after BACKGROUND OF THE INVENTION being cleaned with hydro?uoric acid. Some water can be e?’ectively suppressed by adding a small prior art wafer drying techniques used in manufacturing use amount of hydrochloric acid to control the 0H“ concentra centrifugal spin drying. methods for cleaning rate. The Relevant Technology aqueous hydrochloric acid solution to dry at a controlled In the microelectronics industry. There are no methods currently available which provide for high temperature water rinsing and drying of silicon 65 BRIEF DESCRIPTION OF THE DRAWINGS wafers after being cleaned in HF that result in minimal In order to understand the manner in which the above reoxidation and minimal roughening of the silicon surface. Despite the These and other objects and features of the present roughening effect on Si(100) surfaces. The meth realizing ultraclean silicon Wafers. extended deionized water rinsing which results in reoxida From the foregoing it will be appreciated that an object of tion of the silicon surfaces. or may be learned by water rinses at elevated temperatures. results in roughening on Si(100) surfaces. It is postulated that the large amounts of gaseous water It is well known that the I-[F-last clean is an attractive way 35 bubbling to the surface from either the boiling water or to obtain reduced surface roughening and low metallic boiling aqueous hydrochloric acid solution effectively contamination on silicon surfaces. Field of the Invention after the wafer has been exposed to hydro?uoric acid in The present invention is directed to methods for high order to provide an oxide free silicon surface. One of the most frequently used chemicals in wafer Oxidation of the surfaces of a silicon wafer is minimized cleaning is hydro?uoric (HF) acid. the product yield the surfaces of the silicon wafer is minimized by adding and device performance become even more dependent on ' sufficient hydrochloric acid to water to yield an aqueous the wafer cleaning technology.

surfaces. boiling water. or an aqueous suppression of the reoxidation of the silicon surface in solution of hydrochloric acid having a pH level of about 2. It seems unlikely that the continuous H-passivation observed in boiling water compared to the DETAILED DESCRIPTION OF THE reoxidation observed in hot water and room temperature PREFERRED EMBODHVIENTS water can be explained by the different activation barriers of 45 The present invention is directed to methods for high the individual and chemical pathways. The behavior of silicon surfaces varies signi?cantly in 35 FIG.5. 4a is a pro?le of a wafer treated with room tem cleaned silicon wafers are treated with hot water. An additional. 3 is p-polarized MIR spectra showing the Si—H water surface. FIG. and a wafer boiled in Re-entry of the oxygen in the region of the gas/liquid aqueous hydrochloric acid. the about 70°. removal of the oxi FIG. ?ve minutes in hot water having a temperature of about 80° Prior art methods of rinsing wafers in water after cleaning C. boiling water results from the large amounts of gaseous FIG.397 ' 3 4 obtained. dihydrides and trihy while boiling water treatment yields a rapid etching removal drides are indicated. oxygen within the water. 4b is a pro?le of a wafer boiled in water for about resulting in a faster reoxidation in the hot water than when ten minutes as measured with a Nanoscope IIAtomic Force 30 room temperature water is used.5% HF as a reference. and to room temperature water.681. a surface etch does not stop being cleaned with hydro?uoric acid.5 for about ten minutes. The surface reoxidation is observed in room temperature water. 40 vibration modes of the monohydrides. 5. and a wafer immersed for ?fteen minutes in hot water in aa aqueous hydro?uoric acid solution do not use boiling having a temperature of about 80° C. as M. This acid solution having a pH of about 2. a wafer immersed for surface. Nanoscope 11 Atomic Force Microscope. it also roughens the in the boiling water.133 at 20° C. reference.. a more particular description of the invention been cleaned in an aqueous hydro?uoric acid solution. changes from 14. invention will be described and explained with additional It has been found that the native oxide growth rate on the speci?city and detail through the use of the accompanying wafer surface is dependent on the amount of dissolved drawings list/ed hereinbelow. a wafer boiled in water. When HF 25 FIG. The higher temperature speeds up the surface reaction. 1 is a graph measuring the contact angle as a function dizing species responsible for the silicon surface oxidation of treatment time to indicate the oxidation state of the 10 from the water eliminates the possibility of reoxidation surface of a wafer being treated in either hot water having a during the rinsing and drying step. The brie?y described above will be rendered by reference to the methods of the present invention yield wafers which are appended drawings. The roughening effect of the boiling water on the The anisotropic etching of Si (100) surfaces by methods surfaces of silicon wafers is minimized by adding sufficient of the present invention is enhanced compared to the etching hydrochloric acid to water to yield an aqueous hydrochloric achieved with room temperature water treatment. one of FIG. 2 is a p-polarized multiple internal re?ection (MIR) water bubbling to the surface which effectively pushes the 15 oxygen out of the water. however. by immersing silicon wafers in either boiling water or a previously unrecognized. with H-termination. temperature water rinsing and drying of silicon wafers after In room temperatln'e water. 5 is a comparison of the Si—H stretch modes of boiling water.. factor is the strong temperature boiling aqueous hydrochloric acid solution. D. is relatively small. ' interface is prevented by the escaping gaseous water at the FIG.5. a wafer boiled in water for about ten minutes. The removal of the dissolved oxygen from the 20 boiling water prevents reoxidation of the HF cleaned silicon stretch modes of three wafers including a wafer dipped for six minutes in 0. It seems more likely that the minimal roughening of the surface. Water and do not yield oxide free silica surfaces. a certain amount of oxygen will Force Microscope. be present in the hot water since there is no gas bubbling. and a slow ing a pH level of about 2. Understanding that these drawings su?iciently oxide free that a droplet of deionized water on depict only a typical embodiment of the invention and are one of the surfaces of a silicon Wafer has a contact angle of not therefore to be considered to be limiting of its scope.5% HF as a oxygen from the water is in accordance with Henry’s law. Additionally. The bene?ts of the methods of the barriers since the temperature range of about 80° C.. More particularly. when compared to hot water having a tem three wafers including a wafer treated in room temperature perature of about 80° C. The boiling oxide growth rate. The out di?‘usion of the dissolved spectra of the Si—H stretch vibration modes of three wafers including a wafer dipped for six minutes in 0. respectively. having a perature water as measured with a Nanoscope 11 Atomic temperature of about 80° C.. 4c is a pro?le of a wafer boiled in aqueous hydro ordinary skill in the art would not be inclined to further chloric acid for about ten minutes as measured with a increase the temperature until the water boils. enhancement can be partially attributed to the temperature Oxidation of the surfaces of silicon wafers is minimized dependance of the surface reaction rate. It is postulated that the temperature of about 80° C. to about present invention include an oxide free Si surface with 55 100° C. occurs in hot water than in room temperature water.. the when the native oxide starts to build up on the silicon methods involve treating a silicon wafer with boiling water surface. the vastly diiferent surface water is preferably spiked with sufficient hydrochloric acid processes observed in boiling water treatment and hot water (HCl) to yield an aqueous hydrochloric acid solution having treatment are most likely not caused by the activation a pH value of about 2. absence of reoxidation on the silicon surface in boiling water Immersing silicon wafers in boiling water suppresses is explained by the signi?cant decrease of dissolved oxygen reoxidation of silicon surfaces. to . Accordingly.5. T. The negative the present invention preferably yield wafers having sur logarithm of the ionization constant of water —logKw (where faces with no more oxides than after the silicon wafers have Kw equals [H+][OH']). The methods of dependance of the self-ionization of water. It has been shown that the Si dissolution rate in after the wafer has been exposed to hydro?uoric acid in 50 water is over one order of magnitude higher than the native order to provide an oxide free silicon surface. A water. and a fast surface reoxidation on silicon surfaces is observed in hot wafer boiled in an aqueous hydrochloric acid solution hav water having a temperature of about 80° C. Since faster reoxidation Microscope.

on the silicon surfaces of the wafers.397 5 6 12.5. More particularly.. ecule to attack the Si—Si back-bond at the next level below of the wafers. The terminated surface. The surface passivation of the wafers was A series of experiments were conducted to compare the 45 investigated by making multiple internal re?ection (MIR) surface properties of silicon wafers treated by the methods infrared measurements and then analyzing the silicon of the present invention with the surface properties of silicon hydride stretching modes as well as the relative contribu wafers treated by prior art methods of rinsing and drying tions of the monohydrides. the OH‘conoenhation is about one order of magni with an aqueous hydrochloric acid solution. 35 surface oxidation.5% HF as a minutes to remove the chemical oxide.5. the wafers 15 minutes. A silicon wafer boiled in an aqueous hydrochloric acid It is known that the contact angle changes from 70° to less solution having a pH level of about 2. The results of these experiments are Various parameters in the disclosure novel process are graphically demonstrated in FIG.5 The series of experiments were performed on p-doped percent HF solution to provide a reference. followed by 10 tion during rinsing with hot water having a temperature of an attack of Water on the polarized Si—OH back-bonds. 5. Measurement of the contact angle of a droplet the oxygen insertion. Accordingly. The pH different rinses. rinse wafers in room temperature DI water for a period in the It is postulated that the higher OH‘ concentration in the range of about 1 to 10 minutes to strip ?uoride residues. (100) C2 silicon wafers with a diameter of 125 mm and a 2. A preferred rate at which a EXAMPLE 2 wafer is drawn out of the water solution is about 1 to 5 Experiments were conducted to investigate the surface mm/sec. . and hot water having a temperature of about 80° C. preferred. temperature deionized waterrinsing for a period in the range 65 and the wafer boiled in aqueous hydrochloric acid for about of about 1 to 10 minutes to strip ?uoride residues. Assuming equal [IF] and [OH'] in pure 80° C. hot water.concentra chloric acid solution indicates that minimal surface reoxi tion such that the surfaces of a silicon wafer boiled in dation occurs. The results also indicate that the addition of aqueous hydrochloric acid have a rrns roughness of less than hydrochloric acid to the boiling water has no eifect on the about 0. and about 15 minutes. dihydrides and trihydrides. boiling water. Before the compared to the reference.4 nm. DI water. This allows an OH“ mol angle of a droplet of deionized water on the silicon surfaces . the spectra of the Si-H stretch vibration modes of three wafers wafers were dipped in 0. boiling water accelerates the anisotropic etching and leaves because such a rinse will not cause reoxidation or roughen a rough Si(100) surface by (111) microfacetting. The spectra are shifted along the ordinate for were further immersed in various water solutions. It has been postu EXAMPLE 1 lated that the reaction path involves a slow nucleophilic Experiments were conducted to monitor surface reoxida~ attack of OH‘ on the Si—-H to produce Si—OH. The contact angle decreased quickly boiling aqueous hydrochloric acid solution and drawn from within the 15 minute period as the silicon wafer was the boiling aqueous hydrochloric acid solution than after the _immersed in the 80° C. The wafers ?rst received remains unaltered after the wafers are treated for about 15 a SPM-i-RCA clean which left a chemical oxide on the minutes in the boiling water and in the boiling aqueous HCl surface having a thickness of about 1 nm. including better presentation. The contact angle silicon wafer has been cleaned in an aqueous hydro?uoric 30 remained at approximately 70° for the boiling water and the acid solution. MIR infrared measurements were per treatment in room temperature water. 2 is a p-polarized MIR experiments were performed on the silicon wafers. It is desirable to tude higher in boiling water than in room temperature water. having a pH of about 2. DI water.5 has no surface 25 than 30° when the surface oxygen concentration changes roughening when the silicon wafer has been immersed in the from 0% to near 5%. the wafer boiled in water for about 15 minutes.265 at 100° C. The surface roughening due to the etching boiling aqueous hydrochloric acid solution. The reaction mechanism of water on HF-cleaned bare silicon surfaces is not fully understood. The contact reaction can be e?iectively suppressed by adding a small angle for the boiling water and the boiling aqueous hydro amount of hydrochloric acid to control the OH. A preferred pH level which minimizes roughening passivation of silicon wafers treated in boiling water. After standard room reference.681. As shown in FIG. a is a range of about 1 to 3 pH. formed on a wafer dipped for about six minutes in a 0. MIR infrared measurements were also per of reoxidation and the roughness. boiling aqueous hydrochloric acid solution having a pH EXAMPLES OF THE PRESENT INVENTION level of about 2. the shape and intensity of the silicon hydride signal resistivity between 16 to 24 81cm. and a boiling aqueous hydro has also been postulated that starting with a hydrogen chloric acid solution having a pH level of about 2.5% an aqueous I-IF dip for about 6 including the wafer dipped for 6 minutes in 0. a smooth Si(100) surface can be during the subsequent processes.5 and wafers boiled in water were Wafers were boiled in water and in an aqueous solution of compared with the surface properties resulting from treat hydrochloric acid having a pH of about 2. A preferred immersion time for a wafer is in the range of about 1 to 20 minutes. DI water water. It about 80° C.5 for a period of ment in hot water having a temperature of about 80° C. the Si—~Si back-bond is attacked by the surface reoxidation was tested by measuring the contact dissolved oxygen via insertion. ing of the wafer. 100° C. The surface properties formed on the FTIR after the wafers were treated for about compared in these series of experiments include the amount 55 15 minutes. the level is preferably lowered to 2. At intervals within the 15 minutes rinse. FIG. These postulated roles of OH‘ in of deionized water on wafer surfaces has been demonstrated silicon surface etching are supported by the ?nding that to be a sensitive technique for characterizing surface passi controlling the concentration of OH“ controls the roughness vation after HF treatment and to monitor surface reoxidation of the surface. The silicon wafers. and 100° C. 1. the surface properties of infrared measurements were performed on a Matsen-Galaxy wafers boiled in an aqueous hydrochloric acid solution 50 Fourier Transform Infrared spectroscope (FI‘IR).5 by adding hydrochloric contact angle was measured for a droplet of deionized water acid to the deionized water. realized in boiling water through controlling the 0H“ con 20 The wafers were rinsed for about 15 minutes in the three centration by lowering the pH level of the solution.

therefore. All changes temperature water. This indicates three wafers as measured in the infrared measurements. dihydride. solution.5. wherein the silicon wafer has surfaces also increases the microroughness. The described embodiments are to be considered in all respects only as illustrated and not restrictive. Accordingly. the claims are to be embraced within their scope. By spiking water with su?icient hydro water on one of the surfaces of the silicon wafer has a chloric acid to adjust the pH level to 2. wherein the silicon wafer has substan microroughness of silicon wafers rinsed in either room tially no more microroughness on the surfaces of the silicon temperature water. 5. a smoother surface is obtained when a wafer is boiled in an aqueous peaks decrease with immersion time in the 80° C. Information regarding the the boiling aqueous hydrochloric acid solution than after the microroughness of the silicon wafers can be obtained from silicon wafer has been cleaned in an aqueous hydro?uoric infrared measurements by observing the relative amounts of acid solution. The spectra in FIG. and wafer treated in boiling water. A much higher monohydride peak is observed and a wafer immersed for about 15 minutes in hot water for the silicon wafer treated in boiling water than is observed having a temperature of about 80° C. 3 show that the intensity of the hydride the Si(l00) surface by the OH‘. 4a illustrates the wafer surface morphol acid solution. wherein the surfaces of the silicon wafer wafer immersed in boiling water for 10 minutes. EXAMPLE 4 6.397 7 8 MIR infrared measurements were also performed on three The ly?R spectra obtained from the silicon wafers are wafers including a wafer dipped for about six 6 minutes in shown in FIG. A method of rinsing and drying of a silicon wafer surfaces. The rms roughness was measured for solution. The present invention may be embodied in other speci?c forms without departing ?'om its spirit or essential charac EXAMPLE 3 15 teristics. wherein the silicon wafer has substan of the solution to about 2. boiling water. A method of rinsing and drying of a silicon wafer as temperature of the water from room temperature to boiling de?ned in claim I. or wafer after the silicon wafer has been immersed in the aqueous hydrochloric acid solution having a pH level of boiling aqueous hydrochloric acid solution and drawn from about 2. Silicon wafers were immersed for about 10 minutes in What is claimed and desired to be secured by United room temperature water. 4a with FIG. The an increase in (111) facets due to the anisotropic etching of MIR spectra in FIG. 0.5. indicated by the appended reaction of water on HF cleaned silicon surfaces in room claims rather than by the foregoing description. FIG. D. 4b indicates that 50 5. ogy of the wafer treated in room temperature water.19 nm for the wafer drawing the silicon wafer from the boiling aqueous hydro treated in aqueous hydrochloric acid solution. A method of rinsing and drying of a silicon wafer as illustrates the wafer surface morphology of the surface of the de?ned in claim 1. having surfaces thereon. each of the wafer surfaces and found to be 0. 40 with 4b. the surface contact angle of about 70° after the silicon wafer has been roughening of wafers in boiling water is e?ectively sup 55 immersed in the boiling aqueous hydrochloric acid solution pressed as indicated by comparing FIG.5. and 4 c which are AFM pro?les silicon wafer has been cleaned in an aqueous hydro?uoric of the wafers.5. 4b.5 for about ten minutes. a wafer immersed for about ?ve dride peak positions are indicated by the arrows with either minutes in hot water having a temperature of about 80° C. indicate that wafers boiled in a solution formed by spiking 3. and a boiling aque States Letters Patent is: ous hydrochloric acid solution having a pH level of about 1. 4a are substantially oxide free after the silicon wafer has been illustrates the wafer surface morphology of the surface of the immersed in the boiling aqueous hydrochloric acid solution wafer immersed for 10 minutes in the boiling aqueous and drawn from the boiling aqueous hydrochloric acid hydrochloric acid solution having a pH level of about 2. and trihy 0. wherein the surfaces of the silicon wafer microroughness than immersing a silicon wafer in room are su?iciently oxide free. The microroughness of each wafer after being immersed comprising was directly measured with a Nanoscope II Atomic Force cleaning the silicon wafer in an aqueous hydro?uoric acid Microscope (AFM). The scope Experiments were conducted to investigate the etching of the invention is. 30 The roughness measurements indicate that increasing the 2. shifted along the ordinate for better presentation. FIG.15 nm for the immersing the silicon wafer in a boiling aqueous hydro wafer treated in room temperature water.. A method of rinsing and drying of a silicon wafer as water with su?icient hydrochloric acid to lower the pH level de?ned in claim 1. and 0. comprising: . A method of rinsing and drying of a silicon wafer as Experiments were performed to observe the surface de?ned in claim 1. A method of rinsing and drying of a silicon wafer 2. dihydrides.41 nm for the chloric acidic solution. aqueous hydrochloric acid solution and drawn from the The conclusion based on the rms measurements are boiling aqueous hydrochloric acid solution than after the supported by FIGS. whereby a droplet of deionized temperature water. 4a. and immersing the silicon wafer in the boiling the temperature enhances the anisotropic etching of the aqueous hydrochloric acid solution minimizes oxidation of Si(100) surface.681. 5. The monohydride. boiling water for about ten minutes. boiling water and a boiling aqueous which come within the meaning and range of equivalency of hydrochloric acid solution having a pH level of about 2.5% HP as a reference. 3 are also boiled in water. A method of rinsing and drying of a silicon wafer as immersion of a silicon wafer in boiling water yields greater de?ned in claim 1. FIG. hot water 10 hydrochloric acid solution than is obtained when a wafer is while the OxSiI-I peak can be observed which indicates a fast reoxidation on the surface. and drawn from the boiling aqueous hydrochloric acid solution. FIG. 4b 4. and trihydrides on the silicon 7. Obviously. The microroughness measurements also 35 the surfaces of the silicon wafer. or T. 3 is a p-polarized for the wafers treated in room temperature water or in the MIR spectra of the Si—H stretch vibration modes of these boiling aqueous hydrochloric acid solution. monohydrides. Comparison of FIG.5 have a microroughness compa tially no more oxides on the surfaces of the silicon wafer rable to the microroughness of wafers rinsed in room after the silicon wafer has been immersed in the boiling temperature water. an increase in thereon. an M. chloric acidic solution to dry in ambient air.

wherein the surfaces of the silicon wafer 20 are su?iciently oxide free. wherein the silicon wafer has substan immersing the silicon wafer in a boiling aqueous hydro tially no more microroughness on the surfaces of the silicon chloric acidic solution having a pH level of about 2.5. the boiling aqueous hydrochloric acid solution than after the 8. wherein the silicon wafer substantially cleaning the silicon wafer in an aqueous hydro?uoric acid has no more oxides on the surfaces of the silicon Wafer after solution. whereby the solution. ***** . the silicon wafer has been immersed in the boiling aqueous immersing the silicon wafer in a boiling aqueous hydro hydrochloric acid solution and drawn from the boiling chloric acidic solution having a pH level of about 2. A method of rinsing and drying of a silicon wafer oxidation of the sm'faces of the silicon wafer. the boiling aqueous hydrochloric acid solution minimizes 12. wafer after the silicon wafer has been immersed in the and drawing the silicon wafer from the boiling aqueous hydro boiling aqueous hydrochloric acid solution and drawn from chloric acidic solution to dry in ambient air. whereby a contact angle of about 70° after the silicon wafer has been droplet of deionized water on one of the surfaces of the immersed in the boiling aqueous hydrochloric acid solution silicon wafer has a contact angle of about 70°. A method of rinsing and drying of a silicon wafer as silicon Wafer has been cleaned in an aqueous hydro?uoric de?ned in claim 7. having surfaces thereon.397 9 10 cleaning the silicon wafer in an aqueous hydro?uoric acid 11. and » de?ned in claim 7 . whereby a droplet of deionized drawing the silicon wafer from the boiling aqueous hydro water on one of the surfaces of the silicon wafer has a chloric acidic solution to dry in ambient air. A method of rinsing and drying of a silicon wafer as less than about 0. A method of rinsing and drying of a silicon wafer as solution. A method of rinsing and drying of a silicon wafer as de?ned in claim 7. 5.681. > de?ned in claim 7. wherein immersing the silicon wafer in acid solution.5 aqueous hydrochloric acid solution than after the silicon for a predetermined time su?icient to remove oxide water has been cleaned in an aqueous hydro?uoric acid from the surfaces of the silicon wafer. surfaces of the silicon wafer have a rms roughness of 10. and drawn from the boiling aqueous hydrochloric acid solution.4 nm. comprising: 9.

. 28. line 26. 5. (Sept. Eisenbeerg et al. Mertens. 1997 INVENTOR(S) : UU It is certified that error appears in the above-identified patent and that said Letters Patent is hereby corrected as shown below: Title page .cm- Col. PP 167-170. please insert the following references: J. Proc. line 63. M. PP 485-490.M. Proceedings of the Second International Symposium on Ultra-Clean Processing of Silicon Surfaces." to --Nayami et al. 1994) Col. Mat. Soc. line 23. after "no" insert --more- Col. Heyns. Removal of Metallic contaminants and Native oxide Prom silicon wafer surface by pure water containing a little dissolved Oxygen Mat. Symp. before "The" change ". 4. Res. Symp. 17. line 55. 5.F.5%" insert -of— . H. after "in" change "these" to --this- Col. G." Cover Page.397 Page 1 of 2 DATED Oct. Removal of Metallic Contaminants and Native Oxide from Silicon Wafer Surface by Pure Water Containing a Little Dissolved Oxygen Mat. after "0. H.cm" to -. P. line 59. after "roughening" insert --than- Col.681. Res. Meuris. Effect of Hot Water Exposure 0n Bare Silicon Surfaces in MOS Processing. Proc. line 25. Li. UNITED sTATEs PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO_ 5. item [56] change "Nayami et al. Proc. after "in" change "aa" to --an- Col. 315 (1993) L. Vol. 5. Zou.W.H. Other Publications. Res. Soc. . Bender. 5. Symp. Soc. . . Schmidt and M. 5.

after "15" change "minutes" to --minutc- Signed and Sealed this Thirtieth Day of March. Oct. line 21. 1997 INVENTOR(S) : Li Li It is certified that error appears in the above-identified patent and that said Letters Patent is hereby corrected as shown below: Col. 28. 3 5. 6. 1999 Q. UNITED sTATEs PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO.681. TODD DICKINSON Alias'ling Officer‘ Avring (‘ummirsxs'imu'r of Pawn/x um] 'l'mzlvnmrh .397 Page 2 of 2 DATED .