TWI278927B - Fluid assisted cryogenic cleaning - Google Patents

Abstract

The present invention is directed to fluid assisted cryogenic cleaning of a substrate surface requiting precision cleaning such as semiconductors, metals, and dielectric films. The process comprises the steps of applying a fluid selected from the group consisting of high vapor pressure liquids, reactive gases, and vapors of reactive liquids onto the substrate surface followed by or simultaneously with cryogenic cleaning of the substrate surface to remove contaminants.

Description

1278927 玖, INSTRUCTION DESCRIPTION: TECHNICAL FIELD The present invention relates to a process for cleaning with a fluid or steam, which assists in the removal of semiconductor surfaces or other precision cleaning surfaces by a simultaneous or subsequent low temperature cleaning process. Foreign bodies and pollutants. [Prior Art] The cleaning or preparation of the surface of the wafer substrate with or without various film layers is a key technology in the process of the integrated circuit. In the manufacturing process of integrated circuits, particles and contaminants must be removed from the wafer surface in several important process steps; in the 0.18μιη technique, there are 8 steps in the entire process 400 steps, ie 20% of the manufacturing steps are used Cleaning, various types of membranes, surface shapes, and contaminants that need to be removed during the front-end-of-line (FEOL) and back-end-of-line (BE〇L) cleaning processes, The challenge of cleaning technology is exacerbated, and the removal of particles is an important part of this cleaning process. International semiconductor technology blueprint for the manufacture of defect-free integrated circuits (Intemati〇nai

Technology R〇admap for Semiconductors; ITRS) pointed out that the key particle size is half of the DRAM 1/2 pitch (1). Therefore, at a 13 〇nm technique, the pitch is 130 nm and the critical particle size is 65 nm, so particles larger than 65 nm must be removed to ensure that it is a defect-free device. For small particles, it is difficult to remove these small particles because the ratio of their adhesion to the force of removal increases. For submicron particles, the primary adhesion of the particles to the surface is van der Waals. The adhesion depends on the size of the particles, the distance between the particles and the substrate surface, and the 1278927 constant. The van der Waals force of a spherical particle on a flat substrate can be calculated by Equation 1: where An2 is the Hamaker constant of the system consisting of particles, surfaces, and intervening media; the lanthanide particles are straight from the Z-series particles and the surface. The Hama]<;er constant of the composite system can be calculated from equation (2):

Ai32==Ai2+A33-Ai3-A23 (2) The relationship between the Hamaker constants of two different materials is expressed by the geometric mean AijKA^Ay)"2 of a single Hamaker constant, where Aii and ~ are materials i and The Hamaker constant, in theory, can be calculated using the Lifshitz or London model. Literature [2, 3] provides the Hamaker constant for particles and surfaces used in the fabrication of integrated circuits. When the intervening medium is a fluid, the Hamaker constant value is less than the value of the intervening medium when it is air. Therefore, when there is a layer of fluid between the particles and the surface, the van der Waals force proportional to the Hamaker constant becomes smaller. In addition to the difficulty of removing small particles from the surface, there are various organic and metal organic contaminants that must be removed. In order to achieve faster switching speeds and better circuit performance requirements, new dielectric materials (with dielectric constant <3) and metals are needed to reduce the Rc delay constant in the circuit. The choice of < copper metal system increases the challenge of the integrated system. For the aluminum interconnect (interc〇nnect), the metal patterning is performed by reactive ion etching of aluminum and subsequent dielectric deposition; if copper is used, The dielectric film is first deposited, but then the channels and trenches are formed. Then the steel is deposited in the trenches, and chemical mechanical polishing (CMP) is used to remove excess steel and planarize the surface. Forming a subsequent thin film layer; this method of forming a copper interconnect line in the back-end process (back_end-0f-line; BE0L) is called a double 6 1278927 Dual Damascene process 〇 forming channels and trenches in the dielectric surname Thereafter, a large amount of fluoropolymer residue remains on the surface of the wafer and inside the trench, as shown in the first figure. These residues are generated in the etching process, partly from sidewall erosion caused by non-isotropic etching. The etching residue must be removed before the subsequent thin film layer deposition process. The foregoing thin film layer deposition process includes: copper barrier Ta The /TaN film, the copper seed layer, and finally the trenches are electrochemically filled with copper metal during the damascene process. At present, the size of the trench used in the interconnect in the back-end process is about μ13μηη, which is effective for removing sidewall residues from the inside of the trench during low-temperature cleaning. The size of the low-temperature particle must be less than 0·13μπι, as shown in the first figure. Also shown; these particles must reach the wafer surface at a sufficient rate to produce the momentum transfer required to remove sidewall residues (111〇11161^111:11 transfer). There are three mechanisms for the surface cleaning: the low-temperature particle momentum transfer to overcome the adhesion of the slurry particles to the wafer surface; 2) the removal of particles from the wafer surface by the pulling force of the cleaning gas; and 3) The fluid formed by the interface between the low temperature particles and the surface of the wafer dissolves particles of organic contaminants. In the C〇2 low (10) alpha wash, the airflow at the surface of the wafer creates a boundary layer, [a low temperature particles must pass through the boundary layer to reach the surface of the wafer and the green particles to be removed; during passage through the boundary layer, The gaseous CO2 in the boundary layer generates a tensile force on the low temperature particles, which reduces the velocity. Assuming that the thickness of the boundary layer is h, when the snow particles enter the layer, the vertical component of the velocity must be at least equal to h/t, where t is The time it takes to reach the wafer surface through the boundary layer. The relaxation time of the particles passing through the boundary layer is represented by the following equation (1)·· 0) 9η 7 1278927 where: a is the particle half control^

Pp is the particle density η is the viscosity of the gas

Cc is the Cunningham slip correction factor given in equation (2)

Cc=l+1.246(X/a)+0.42(^/a)exp[-0.87(aA^)] where the mean free path of the λ-type gas molecules. Since the low temperature cleaning system is carried out under atmospheric pressure, the Cunningham slip correction factor is 1 in the equation (1) for low temperature particles having a size larger than 0·1 μπι. Therefore, in order for the C〇2 snow-like particles to have sufficient momentum to remove foreign matter from the wafer surface and the inside of the trench, the time to pass through the boundary layer must be less than the relaxation time, in which case the speed at which it reaches the surface is greater than 36% of the starting speed. Equation 1 shows that the relaxation time is shortened with the particle size. Therefore, particles of smaller size cannot reach the surface of the wafer at a sufficiently large speed, and thus the submicron channels and the inner walls of the trenches cannot be effectively cleaned. The prior art method generally uses C〇2 or argon low-temperature spraying to remove foreign matter from the surface, for example, "spray surface treatment" of U.S. Patent No. 5,931,721, and "substrate cleaning method and apparatus" of U.S. Patent No. 6,036,581. U.S. Patent No. 5,853,962, "Using Carbon Dioxide Ejection to Remove Photoresist Layers and Re-Deposition", U.S. Patent No. 6,203,406, "Spray Surface Treatment" and U.S. Patent No. 5,775,127, "Highly Dispersed Carbon Dioxide Snow Making Apparatus"; All of the above prior art patents remove foreign matter from a flat surface by the physical force transmitted by momentum to the contaminants. Since the adhesion between the contaminant particles and the substrate is large, the prior art method 1272827 can effectively remove particles smaller than 〇·3μηι; moreover, these cleaning methods do not have a groove effect with a high aspect ratio. For example, in the latter stage of the integrated device process, the channels and trenches are manufactured to remove submicron small particles and complex polymer residues generated during the process (for example, dielectric stamping). U.S. Patent No. 6,332,470, "Spray Substrate Cleaner" discloses the use of steam alone or in combination with high pressure droplets to clean a semiconductor substrate; unfortunately, the fluid does not have as much impact as solid C〇2. The momentum transfer capability does not effectively remove small sized particles. U.S. Patent No. 5,9,8,510, "Removing Residues by Supercritical Fluids" discloses the use of cryogenic sprays in combination with supercritical fluids or liquid C〇2, but due to c〇2 & non-polar molecules' The dissolving power of the foreign matter is greatly reduced; in addition, since the formation of fluid or supercritical c〇2 requires high pressure (fluid needs to be greater than 75 psi and supercritical fluid needs to be greater than l 〇 80 psi), the device is also very expensive. U.S. Patent No. 6,231,775 teaches the use of sulfur dioxide gas alone or in combination with sulfur trioxide and other gases to remove organic matter from the substrate in the ashing (four) (iv) weighting. However, the vapor phase cleaning cannot remove the use of low material (for example: A typical dual damascene build-up process for carbon-doped oxides) forms a crosslinked photoresist layer during etching. Due to the shortcomings of the prior art, there is still a need for a highly efficient method for removing contaminants more efficiently, including surfaces from semiconductor wafers, metal films, other substrates requiring precision cleaning, and high depth and width (10), including impurities. , foreign matter, chemical residues _ and uniform or non-uniform contaminants consisting of crosslinked and bulk photoresist layers, post-soil residues and submicron sized particles. SUMMARY OF THE INVENTION The present invention provides an improved method of surface I, which is required to be cleaned on the surface of a substrate to be washed 1278927 (for example, a semiconductor, a metal, and a dielectric film). SUMMARY OF THE INVENTION The present invention comprises a cleaning method for removing contaminants from the surface of a substrate requiring precision cleaning, which can be used at low wash or simultaneously with low temperature cleaning to remove foreign matter and contaminants on the surface of the substrate. The cleaning method of the Lisa can use a fluid selected from the group consisting of a high pressure vapor fluid, a reactive gas, or a vapor of a reactive fluid depending on the contaminants to be removed from the surface of the substrate. The fluid is maintained in contact with the surface for up to 2 minutes to form an environment that removes contaminants from the surface of the substrate or reduces the adhesion of contaminants to the surface so that it can be removed during subsequent low temperature cleaning. [Embodiment] Fluid-assisted cleaning method and example The fluid used in this example is a high-pressure vapor fluid, which can reduce the van der Waals force of foreign matter and the surface of the substrate (such as semiconductor wafers or thin county surfaces). The high-pressure steam is sprayed onto the surface of the substrate, and the initially injected fluid reduces the van der Waals force, thereby making it easier for subsequent low-temperature cleaning to remove foreign matter from the substrate surface; if the upstream program before the low-temperature cleaning is a water phase procedure, The fluid also removes most of the water prior to the low temperature cleaning, as in the copending U.S. Patent Application Serial No. 10/215,859. In addition, the high pressure steam can be used to dissolve organic contaminants from the surface, and a specific high pressure vapor fluid can be selected according to the organic contaminants contained on the surface of the substrate; those skilled in the art should be aware of fluids capable of dissolving common organic contaminants. Types of. High pressure steam stream systems suitable for use in the present invention 47 include, but are not limited to, ethanol, propane, ethanol acetone mixtures, isopropanol, methanol, decyl methacrylate, methyl iodide, ethyl bromide, acetomtnle, Methane, pyrrolidine (Udine) and tetrahydrofuran (tetrahydr〇fo 10 1278927 and 'any fluid with high vapor pressure can be used. High pressure steam fluid can easily be released from the surface of the substrate' does not require heat drying Or rotating the substrate to dry; the fluid preferably has a low freezing point and has a polarity in itself, and the low freezing point of the fluid ensures any residual fluid remaining on the surface of the wafer during low temperature cleaning, without wafers during low temperature cleaning The temperature drops and solidifies; the polarity of the fluid helps dissolve the organic or inorganic contaminants on the surface of the wafer; the pressure of the high-pressure vapor fluid is at 25° (: preferably greater than 5 kPa, and the freezing point is preferably less than -50) °C, and its dipole moment is preferably greater than 1.5D. High pressure vapor fluid can be used on any substrate surface that requires precision cleaning. However, preferred surface systems include: semiconductor surface, gold And a dielectric film. Therefore, the terms "semiconductor", "metal film", "dielectric film" or "wafer" as used herein mean that the same procedure can be applied to other substrate surfaces, including compound semiconductors. (C〇mpOUIKj§;emic〇ncjuct〇r) hard disk media, optical components, GaAs substrates, and films in the fabrication of components. The examples and embodiments provided herein are not intended to limit the invention. For example, the high pressure vapor fluid is sprayed onto the surface of the semiconductor wafer at a temperature of 30 to 50 ° C, and the ejected fluid may be a thick film or a thin layer, and the layer preferably has a thickness of at least 5 Up to 1 A, and preferably a Teflon-made spray nozzle for use in a wet cleaning station that sprays deionized water onto the wafer surface, but any other nozzle used in the art may be used. Preferably, the surface of the wafer is covered by the fluid for at least one minute, and if the moonlight is covered for ten minutes, the fluid may be sprayed only once or multiple times to ensure that the surface of the wafer remains wet; Similarly, when the fluid is ejected, the wafer can be rotated at a speed of about 100 rpm to ensure uniform coverage of the fluid on the surface of the wafer. 1278927 After the wet period, the low temperature jet can be carbon dioxide, nitrogen or this technology. Other gases well known in the art, and any well known cryogenic cleaning technique can be used. An example of co2 cryogenic cleaning will be described below. The initial result of the spray seam vapor fluid is reduced.

The Hamaker constant, which in turn reduces the van der Waals force, sprays the fluid to reduce the adhesion of contaminants to the wafer surface. The smudge is more visibly removed than the cryogenic cleaning process alone. In addition to the aforementioned cleaning procedures, the high pressure vapor fluid can also be used simultaneously with low temperature cleaning. For example, 'in this case, the second nozzle for spraying the high-pressure vapor fluid is installed with the first nozzle for c低温2 low-temperature cleaning, and the higher the high-pressure vapor of Confucian is formed, the thinner layer is formed. The C〇2 low temperature cleaning is continued while the fluid is sprayed onto the substrate. The process of removing particulate contaminants by low temperature cleaning is significantly improved by the use of the south vapor fluid. The second figure shows the difference between the particle removal efficiency and the particle size in the fresh low temperature cleaning and the flow-through temperature cleaning. For the cleaning of the county with a size smaller than (4), compared with the standard C02fe temperature cleaning program, the fine flow The low-temperature cleaning procedure can be significantly improved; when the particle size is between 〇·98μπι and 2·50μηι, there is no significant difference between the use of the fluid-assisted low-temperature cleaning process and the standard C〇2 low-temperature cleaning process. Steam-assisted cleaning and examples Reactive steam from reactive gases or fluids can be used to help remove contaminants. Reactive gas or helium vapor is usually used to remove the organic photoresist layer on the surface of the substrate and the etch residue of the fluoropolymer inside the trench, which can be selected according to the reactivity with the surface of the substrate; Preferably, the gas/steam produces by-products in the form of a gas. (For convenience of reference, the reactive gases mentioned in the following t. 12 1278927 (4) book t may include reactive vapors of the fluid, and the reactive vapors mentioned may all include reactive gases.) Cleaning in semiconductor wafers In the process, the pollutants to be removed include not only particulate pollutants, but also the front-end engraving ontof4ine in the manufacture of microelectronic components and the organic, inorganic and metallic residues produced in the subsequent stages of the process. (4) The physical mechanism Wei removes these membranes, so the physical machine 雠敎 chemical square wire to be removed is required to meet the requirements of Qing (4). In the present invention, the 'ru phase cleaning is a chemical cleaning method, and the low temperature cleaning is mainly a physical cleaning;

The two methods are performed sequentially or sequentially to completely remove uniform or non-uniform contaminants. An example of a reactive vapor that can be applied to the process of the present invention can be a vapor of a high pressure vapor stream comprising acetone, a mixture of ethanol and acetone, isopropanol, methanol, formic acid, a moth, and a moth. May include - gas, such as: ozone, water vapor, nitrogen, gas, nitrogen trifluoride, helium, argon, helium, sulfur trioxide, oxygen, fluorine or fluorocarbon gas or gas Combination; the gas or vapor should be compatible with the internal organic photoresist layer and fluoropolymer

The contact residue (4) reacts; moreover, the by-product of the reaction is preferably in a domain state, so that it can be removed from the cleaning f by a nitrogen stream. (4) Gas and fluid vapors include isopropanol, ethanol propionate mixture, decyl alcohol, ozone 'steam, nitrogen trifluoride, sulfur trioxide, oxygen, gas and carbon gas compounds. .. During the rear side cleaning process, the low temperature particles cannot enter the channels with high aspect ratio and the inside of the ditch. Therefore, it is necessary to have a face or steam to effectively expand the ship_trench. The body or vapor then chemically reacts with the residue of the polymer to convert it into a gaseous by-product which can be removed by a stream of nitrogen flowing through the surface of the substrate; alternatively, it can be introduced into a low pressure separation chamber , 13 1278927 The gas/vapor phase reaction in the cleaning chamber is carried out at temperatures up to 200 °C. After this cleaning process, the wafer can be transferred to a second cleaning chamber at atmospheric pressure where it is cryogenically cleaned. This vapor can condense on the surface of the wafer during this process. By selecting the appropriate vapor, the condensing process also reduces the Hammaker constant, which in turn reduces the adhesion of the particles to the surface, and thus the condensation process also aids in the removal of particles by cryogenic cleaning. The gas or vapor can be further utilized by using a free radical initiator (eg, producing ultra violet light, X-ray, excimer laser for reactive chemical species). , coronadischarge or plasma to produce chemicals that enhance reactivity with contaminants to be removed, combined with physical cleaning of snow or low temperature spray to remove non-reactive contamination Things. In wet cleaning and dual-frequency plasma cleaning, the same cleaning mechanism can be seen. 'Double-frequency plasma cleaning uses downstream MW plasma to generate chemicals to react with contaminants, and RF plasma to generate ion bombardment. . In one embodiment of the present invention in combination with C〇2 cryogenic cleaning, the fluid vapor is injected through a nozzle mounted on the same arm as the C〇2 cryogenic nozzle. The nozzle may be a 1/4 to 1/2 inch diameter stainless steel orifice or a specially designed nozzle having a corona discharge line along the shaft for inducing discharge in the vapor, and the nozzle It is preferable to form about 10 with the surface of the substrate. To 90. The vapor is also ejected through a sprinkler located above the surface of the substrate to ensure uniform coverage of the surface of the substrate; during vapor release, the substrate is preferably maintained at the same temperature as the vapor, if condensation is required. The substrate temperature can be kept below the steam temperature to cause vapor condensation and form on the substrate © liquid_H If the reactivity of the vapor is insufficient to react with a given type of soil, the steam can be added by means of a radical initiator Reactive; steam 14 1278927 Swarovski substrate table _a bribe for twenty minutes, the process is continuous or intermittent touch; it is best to only turn the steam - _, but if necessary, can use the steam mixture at the same time Remove contaminants. According to the tree _reaction test or jetting, it can be carried out with the low-temperature cleaning side-cleaning chamber or the knife-opening/month washing chamber, and the low-temperature cleaning can be performed simultaneously with the use of reactive gas or hunger, or Immediately after the New Zealand; according to Gu's reactive gas or steam, such as water steam a, the farm cleans the steam cleaning chamber before the start of low temperature cleaning. Due to the use of reactive gases or vapors, the removal of contaminants, especially the removal of the grooves after etching of the substrate surface, is improved. The cleaning wire is beneficial for the contamination of the homogenous sentence, such as the residue film on the side of the ipi and the side wall of the trench or the photoresist layer residue behind the side. Example Standard <: 〇 2 Low Temperature Cleaning Standard low temperature cleaning is performed regardless of whether the hydrazine is carried out after the fluid cleaning process or at the same time. U.S. Patent No. 5,853,962 discloses a standard (χ>2 low temperature cleaning process, which is incorporated by reference. The second drawing is a typical C〇2 low temperature cleaning system embodiment: the cleaning container 12 provides an extremely clean, sealed or sealed a cleaning area in which the wafer cassette is fixed to the platen 2 by vacuum, the platen and the wafer being maintained at a control temperature of up to 1 〇〇〇c; first, the temperature is room temperature, pressure The 850 psi CO 2 fluid is passed through a sintered coaxial filter 4 to filter out very small particles to make the carbon dioxide as pure as possible and reduce contaminants in the liquid stream; then, the C〇2 fluid is expanded through a small orifice nozzle, the nozzle Preferably, the diameter is from 〇.〇5 inches to upper 吋, the rapid expansion of the fluid causes a temperature drop, resulting in the formation of solid CO 2 snow particles that are entrained at a flow rate of about 1 to 3 cubic feet per minute. 2 In the gas stream, let the solid and gaseous CO 2 15 1278927 flow flow to the wafer surface at an angle of about 30 to 60 (preferably about 45.), and the nozzle is preferably placed on the nozzle observation line to the wafer surface. a position of about 0.375 inches to 0.5 inches; during cleaning, the platen 2 moves back and forth along the y direction on the track 9, and the arms of the cleaning nozzle move linearly along the X direction on the track 10, and the result is in the crystal. The circular surface creates a grid-like cleaning pattern, and the step size and scanning speed of the platen 2 and the nozzle arm can be preset as needed; the humidity of the cleaning chamber should be kept as low as possible, for example, <-40 ° C Dewpoint, which can be maintained by flowing nitrogen or clean dry air. Low humidity prevents condensation and solidification of water in the atmosphere during cleaning. These condensation and solidified water will be contaminated. The particles form crystalline bridges on the surface of the wafer to increase the adhesion between the contaminated particles and the wafer. Moreover, it is important to neutralize the electrostatic charge in the cleaning chamber throughout the cleaning process. A bipolar corona ionization bar 5 is available for this purpose; the system is also equipped with a nozzle (Polonium nozzle) behind the c〇2 nozzle for enhancing the wafer mounted on a ground plate Electricity Neutralization; the generation of static charge is caused by frictional electricity generation at the mouth and wafer surface during C-channel, and is enhanced by the low humidity in the cleaning chamber. For particulate pollutants, the removal mechanism is mainly through CO2. The momentum transfer of the low temperature particles overcomes the adhesion of the contaminant particles to the surface of the wafer. Once the particles are "loose", the tensile force of the gaseous (7) 2 will be removed from the surface of the crystal S1. The cleaning mechanism of the organic thin film contaminants is due to the low temperature c〇 The impact pressure on the surface of the wafer, while in the organic contaminant and the surface of the filament, the C〇2 fluid can then dissolve the organic contaminant and carry it away from the wafer surface. The embodiments of the present application and the embodiments are intended to illustrate the present invention, and are not intended to limit the present invention to those skilled in the art, without departing from the spirit and scope of the present invention, when it is possible to use 16 1278927 In other implementations. Such embodiments are included within the scope of the invention. References [1] . International Technology Roadmap for Semiconductors 2001 Edition [2] . Handbook of Semiconductor Wafer Cleaning Technology Science,

Technology and Applications, Edited by Wemer Kern, Noyes Publications, 1993 [3] . Particle control for Semiconductor Manufacturing, Edited by R. P.

Donovan, Marcel Dekker Inc., 1990

17 1278927 [Simple description of the diagram] The first figure shows the cleaning of the residue after etching in the double damascene structure. The left image is an SEM image of the trench etched structure with the remnant residue. The image on the right shows the SEM image of the structure of the ditch after the completion of the sequence of plasma and wet cleaning steps. The second graph shows a comparison chart of the relationship between particle removal efficiency and particle size in standard low temperature cleaning and this fluid assisted low temperature cleaning. The third figure shows a schematic of a conventional C〇2 cryogenic cleaning system. [Component Symbol Comparison Table] 1 - Wafer 2 - Taiwan Counter 3 - Nozzle 4 - Sintered Coaxial Filter 5 - Bipolar Corona Ion Rod 6 - Ultra High Efficiency Filter (Ulpamter) 9 - Essence 10- Essence 12 - Cleaning Container

Claims (1)

1278927 Pickup, Patent Application Range: 1. A method for removing contaminants from the surface of a substrate that requires precision cleaning, comprising the steps of: (a) spraying at least one fluid onto the surface of the substrate, wherein the flow system is selected from the group consisting of : high pressure steam fluid, reactive gas and reactive fluid vapor; and (b) low temperature cleaning of the substrate surface to remove contaminants. 2. A method for removing contaminants from a surface of a substrate requiring precision cleaning as described in claim 1 wherein steps (8) and (b) are carried out simultaneously. 3. The method for removing contaminants from the surface of a substrate requiring precision cleaning as described in claim 1 wherein steps (a) and (b) are carried out sequentially. 4. The method for removing contaminants from the surface of a substrate requiring precision cleaning as described in claim 1, wherein the high pressure steam flow system may be selected from the group consisting of ethanol, propylene glycol, ethanol acetone mixture, and different Propanol, methanol, methyl formate, methyl iodide, ethyl bromide, cyanide, chloroform, ratio of tetrahydrofuran and mixtures thereof. 5. The method of removing contaminants from a surface of a substrate requiring precision cleaning as described in claim 1, wherein the vapor of the reactive fluid is a fluid selected from the group consisting of ethanol, acetone, and acetone. Mixture, isopropanol, methanol, methyl formate, ezrin, ethyl bromide and mixtures thereof. 6. The method of removing contaminants from a surface of a substrate requiring precision cleaning as described in claim 1, wherein the reactive gas system may be one or more gases selected from the group consisting of ozone, water vapor, Hydrogen, nitrogen, nitrogen oxides, nitrogen trifluoride, helium, argon, helium, sulfur trioxide, oxygen, fluorine or fluorocarbon gases and mixtures thereof. 19 1278927 7. The method for removing contaminants from the surface of a substrate requiring precision cleaning as described in claim 1, wherein the aforementioned reactive gas or vapor system may be selected from the group consisting of: a mixture of iso---co-ethanol acetone , methanol, ozone, water vapor, nitrogen trifluoride, sulfur trioxide, oxygen, gas, fluorocarbon gases and mixtures thereof. 8. A method of removing contaminants from a surface of a substrate requiring precision cleaning as described in claim 1, wherein the fluid is maintained in contact with the surface of the substrate for 10 minutes before the low temperature cleaning is initiated. 9. The method of removing contaminants from the surface of a substrate requiring precision cleaning as described in claim 8 of the patent application, wherein the fluid is kept in contact with the surface of the substrate for less than 2 minutes before starting the low temperature cleaning. 10. The method of removing contaminants from a surface of a substrate requiring precision cleaning as described in the scope of claim 2, wherein the contaminant size is less than 〇·76 μπι. 11. The method for removing contaminants from the surface of a substrate requiring precision cleaning as described in claim 1, wherein the contaminant size is less than 0·13 μπι ° 12. as described in claim 1 A method of removing contaminants from a surface of a precision cleaned substrate, wherein the aforementioned high pressure vapor fluid is at 25. (The vapor pressure is about 5 kPa and the freezing point is about -50 ° C. 13. The method for removing contaminants from the surface of the substrate requiring precision cleaning as described in claim 1 wherein the high pressure steam fluid Having a dipole moment greater than 丨·513. 20 127^927 14. 15. 16. 17. 18. 19. Method for removing contaminants from the surface of a substrate requiring precision cleaning as described in claim 1 The above-mentioned high-pressure vapor fluid is maintained on the surface of the substrate to a fluid layer of j 5A and maintained within 1 minute, preferably less than 2 minutes, before starting the low-temperature cleaning. The method of removing contaminants from the surface of a substrate requiring precision cleaning, wherein the foregoing method may further comprise the step of removing a large portion of water from the surface of the substrate by the high pressure vapor fluid. The precision cleaning is required as described in claim 1 The method for removing contaminants from the surface of the substrate, wherein the surface of the substrate is a semiconductor, a metal or a dielectric film. The substrate required for precision cleaning as described in claim 1 The method for removing contaminants, wherein the foregoing flow system is a reactive gas or steam, which reacts with the dirt on the surface of the substrate to form a volatile gaseous by-product; the foregoing method is further included before the low temperature cleaning is started, a step of removing a reactive gas or vapor from the surface for up to 2 minutes and removing the gaseous by-product. The method of removing contaminants from the surface of a substrate requiring precision cleaning as described in claim 17 of the patent scope, wherein the aforementioned reactivity The gas or steam is introduced into a cleaning chamber containing the substrate at a low pressure and/or at a temperature of up to 200° C. The method for removing contaminants from the surface of the substrate requiring precision cleaning as described in claim 18, Wherein the foregoing method comprises a method of cleaning the cleaning chamber to remove by-products by using nitrogen or clean dry air. For example, the method for reducing contaminant-removing contaminants from the sub-cleaning base according to Item 17 of the full-time application, wherein the foregoing The method comprises spraying the reactive gas or steam onto the surface in the presence of a radical from 21 20. 1278927 to the surface to Reactive chemical by-products of gaseous or vapors and contaminants. 21. A method for removing contaminants from the surface of a substrate requiring precision cleaning as described in claim 20, wherein the radical initiator system described above For far ultraviolet light, X-ray, laser, corona discharge or plasma. twenty two