CN101049598A - High-pressure wet cleaning method - Google Patents
High-pressure wet cleaning method Download PDFInfo
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- CN101049598A CN101049598A CN 200610025418 CN200610025418A CN101049598A CN 101049598 A CN101049598 A CN 101049598A CN 200610025418 CN200610025418 CN 200610025418 CN 200610025418 A CN200610025418 A CN 200610025418A CN 101049598 A CN101049598 A CN 101049598A
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Abstract
A high-pressure cleaning method includes such steps as putting a workpiece to be cleaned in a sealed cavity, making the workpiece to rotate, introducing a fluid to the surface of said rotating workpiece to form a thin layer, filling the ozone gas in said sealed cavity while increasing its pressure to make to ozone gas pass through said fluid layer onto the surface of said workpiece, and oxidizing the pollutant for removing it.
Description
Technical field
The present invention relates to a kind of high-pressure wet cleaning method.In particular to improve ozone (O by high pressure
3) thereby diffusion in the washing fluid boundary layer improves the method for cleaning efficiency, wherein said washing fluid comprises hydrofluoric acid (HF), the deionized water (DIH of heating or vaporization
2O) etc.
Background technology
Process for fabrication of semiconductor device depends on the chemical oxygen voltinism solution of wet type for a long time and removes photoresist and other impurity, and these impurity can be graininess foreign material, metal, organic matter and/or natural oxide etc.In forming the FEOL (FEOL) of grid, transistor and capacitance structure, be used to remove photoresist and the modal wet chemistry preparation of organic washing is a kind of sulfuric acid-mixed solution of hydrogen peroxide, be known as " piranha " or " SPM ".
Use the concrete device that needs prepare that how much depends on of processing step that SPM solution cleans, generally include 15 to 30 steps, complex process and bring variety of issue easily and increase the ratio of defects of product.And, working concentration is tens percent high-concentration sulfuric acid. mixed solution of hydrogen peroxide needs a large amount of medicaments (sulfuric acid and hydrogen peroxide) and a large amount of high purity water that washes usefulness afterwards that cleans, so not only increased preparation sulfuric acid. the cost of the required medicament of mixed solution of hydrogen peroxide, also increased sulfuric acid-mixed solution of hydrogen peroxide waste liquid and the used high purity water of flushing process have been handled the required extensive waste liquid and the demand of sewage treatment equipment, and increased equipment assembling and operating cost, thereby cause the manufacturing cost of required device to improve.But also to have ventilation unit to discharge the purge chamber with the cleaning agent steam that the high temperature cleaning process is produced, thermal source and ventilation unit also can cause cost to increase.
In current microelectronic industry, people pay close attention to how to reduce operating cost to improve profit, and this needs to adopt the technology that reduces ratio of defects and raise the efficiency undoubtedly.And the demand of the variation of designs and environmental sound technology has also promoted the further improvement of people for wet cleaning.The method that one verified has good rate of return on investment and can improve device performance just is to use ozone and water, for example, someone has proposed the method for using dissolved ozone concentration to clean at ambient temperature as the high purity water of 2-10ppm ten minutes, but this method also has problems, decompose if the organic matter that adheres to is too many or difficult, it is also very difficult thoroughly to remove organic matter, to such an extent as to even through after long-time the cleaning, also have the possibility of the organic substance residues that adheres to.
Therefore, people have carried out various trials for using ozone and water to clean, and comprise attempting to increase the ozone of solubility to dissolve in the maximization water by reducing water temperature, because the solubility of ozone depends on temperature consumingly and reduces with the rising of temperature.But the temperature reduction can make that cleaning rate is too slow and inefficent.
1997, Semitool company developed a kind of HydrOzone of being called
TMTechnology, it has adopted a kind of distinguished method.The target of these research and development is to make the maximizing efficiency of ozone rather than make its solubility maximization in water.The key that ozone can efficiently clean does not lie in to the full extent ozone is sent to water surface, and is the accessory substance that ozone in water decomposes.The electrochemical potential of ozone is a tolerance to cleansing power, and the electrochemical potential of free hydroxyl (OH) is more taller than ozone.These hydroxyls produce in the ozone decomposable process, and they are extremely important for effective cleaning, and it is very favorable therefore making the hydroxy radical content maximization.The speed that ozone decomposes in water almost is spontaneous, can form intermediate material rapidly simultaneously, hydroxyl produces fast as a kind of intermediate product, in the time frame of microsecond, resolve into other invalid materials then again, so, the problem of most critical is to produce hydroxyl in the position of needs as much as possible, can utilize its reactivity so most effectively.HydrOzone technology is based on this principle, and ozone is on the position that needs, and provides the water of vaporization or HF to come catalysis to impel ozone to resolve into active material then, thereby very effectively utilizes ozone.
Tradition HydrOzone method is that wafer is rotated a process cavity of having injected dry ozone gas, simultaneously with the surface of high-temperature water spray painting to wafer.Usually, will about 240g/m
3High-concentrated ozone be injected in the process cavity, simultaneously water is sprayed onto the surface that rotates wafer with the form of water smoke or aerosol.The rotation of wafer adds appropriate water discharge rate, can produce a thin boundary layer; In this thin layer, ozone reacts and produces active material and clear the pollution off.At high temperature react the hydroxyl that can produce higher concentration and reaction rate faster.Therefore, HydrOzone technology is to carry out under 95 ℃ temperature.(referring to U.S. Pat 2001042555, US2002050279 and US2003205240)
Use the technology of ozone and water, HydrOzone for example, will reduce the impurity metal ion relevant with the traditional chemical material with elimination, thereby help improving the breakdown voltage of the capacitance structure that cleans, and because the chemical reagent of HydrOzone technology only uses once process stabilizing between therefore different wafers.In addition, do not adopt the conventional clean chemical reagent, eliminated substantially or reduced chemical waste in a large number, this has not only reduced manufacturing cost, and has reduced the influence to environment.
Yet, the technology of using ozone and water up to now still can not be enough effectively replace solution clean and clean as SPM, so people have carried out and tested in a large number, hope can further improve cleaning efficiency by adjusting ozone flow, reaction temperature and other electrochemical conditions.
Summary of the invention
In order further to improve cleaning efficiency, the present inventor studies at the ozone concentration that how further to improve near surface to be cleaned, thereby finds that the raising gas pressure can improve the diffusion of ozone in the washing fluid boundary layer and can effectively obtain high ozone concentration.The present invention just is based on that this result finishes.
Therefore, the objective of the invention is to propose a kind of high-pressure wet cleaning method, the cleaning process that it is characterized in that wetting is carried out under the condition that has high-pressure ozone gas.
Preferably, high-pressure wet cleaning method according to the present invention may further comprise the steps:
(1) workpiece to be cleaned is placed the airtight process cavity of high-pressure ozone;
(2) make described workpiece rotation;
(3) fluid is incorporated into the surface of rotational workpieces, to form thin boundary layer at surface of the work;
(4) in described process cavity, inject ozone gas, and increase the air pressure of ozone in the described process cavity, make ozone gas diffuse to surface of the work by the boundary layer, thereby with the pollutant oxidation of surface of the work and remove.
According to high-pressure wet cleaning method of the present invention, wherein said workpiece comprises the semiconductor devices that all need clean, especially silicon wafer.
According to high-pressure wet cleaning method of the present invention, wherein said fluid is preferably the water or the hydrofluoric acid of heating or vaporization, more preferably Qi Hua water.
According to high-pressure wet cleaning method of the present invention, also comprise the step that fluid is heated to 26-200 ℃, when described fluid is water, preferably be heated to 90-100 ℃, most preferably be 95 ℃.
According to high-pressure wet cleaning method of the present invention, also comprise by the rotary speed of adjusting workpiece and/or the step that described flow rate of fluid is controlled boundary layer thickness.
According to high-pressure wet cleaning method of the present invention, wherein preferably described fluid is ejected into surface of the work.
According to high-pressure wet cleaning method of the present invention, wherein be injected into ozone in the described process cavity preferably through the ozone gas of super-dry.
According to high-pressure wet cleaning method of the present invention, the air pressure of ozone is at least 1 atmospheric pressure in the wherein said process cavity, be preferably at least 2 atmospheric pressure, more preferably at least 3 or more a plurality of atmospheric pressure, as long as the increase of air pressure can not cause workpiece or equipment etc. that other remarkable disadvantageous variations take place.
Preferably, in cleaning process the air pressure in the airtight process cavity of high-pressure ozone is monitored, in time the used up ozone of compensation is stablized to keep the technological parameter in the cleaning process.
Compare with traditional method, the advantage of high-pressure wet cleaning method of the present invention is to significantly improve process efficiency, can utilize the shorter time to reach identical with still less chemical substance or even better cleaning performance, thereby improve the environment friendly and the high benefit of cleaning.
In general, the air pressure that is provided is big more, cleaning efficiency is also high more, and the two almost is proportional increase, and this can make an explanation by following theory.
Understand easily, the ozone concentration that is dissolved in the fluid increases with the ozone concentration of flow surface and the increase of the diffusion flow of ozone in fluid.According to the Fick law, diffusion mass flow Г=-c n, wherein c is a diffusion coefficient, and typical temperature is high more, and diffusion coefficient is big more, and vice versa; n is the concentration gradient of component on dispersal direction.Clearly, the diffusion mass flow is directly proportional with diffusion coefficient and concentration gradient.Based on the law of thermodynamics, be assumed to be constant temperature process, then can improve diffusion coefficient, thereby obtain higher ozone concentration by increasing pressure.
In water boundary layer, be diffused as example with ozone, as shown in Figure 1.
Be similar to according to one dimension, suppose the O of boundary layer upper surface and workpiece surface
3Concentration is respectively O
3sAnd O
3b, and suppose that gas is perfect gas, promptly concentration should be O
3s=P/RT.O
3The flow that flows to workpiece surface can be shown below:
Г＝D(O
3s-O
3b)/L，
Wherein D is a diffusivity, is proportional to temperature; L is a boundary layer thickness.
Under 298K, atmospheric pressure, D=0.24 * 10
-8m
2/ s, the value of L is generally 1mm.O
3bBe constant (the supposition quality is transmitted limited, is 0).When pressure is 1Bar, O
3Concentration is 2.1kg/m
3(about 660mol/m
3), this moment Г=0.24 * 10
-8 * 660/0.001[mol/m
2S]=0.0016[mol/m
2S].Mass flow in the time of in like manner can getting pressure and be respectively 2Bar, 3Bar, as shown in Figure 2.Clearly, the mass flow of ozone increases and linear the raising with air pressure.
Description of drawings
Fig. 1 illustrates the diffusion schematic diagram of ozone in water boundary layer.
Fig. 2 illustrates the diffusion mass flow that shows ozone and increases and the linear curve that improves with air pressure.
The specific embodiment
With the present invention will be described in more detail, still the invention is not restricted to this below.
Carry out the wet illustrative methods of cleaning of high pressure carries out according to following steps according to the present invention.
At first, silicon wafer to be cleaned is placed standard polytetrafluoroethylene (PTFE) wafer case, and put into the airtight process cavity of high-pressure ozone and make its rotation.Scheme also can place silicon wafer to be cleaned the centrifugal treating chamber of utilization " carrier-free " rotating shaft design as an alternative, puts into the airtight process cavity of high-pressure ozone again and makes its rotation.
Washing fluid is preferably steam and is ejected into silicon wafer surface.So not only heated silicon wafer surface, environment temperature is raise.Can form the very thin liquid film of one deck at silicon wafer surface when stopping to spray, be called the boundary layer.Control boundary layer thickness by the rotary speed of adjustment silicon wafer and/or the injection program of steam, preferably be controlled at about 1mm.
Meanwhile, in described process cavity, inject ozone gas.Ozone gas can utilize ozonized gas generator to produce, and can inject by the pipeline of injection water steam, also can inject by the pipeline that is different from this pipeline.When stopping water-vapour spray, can continue to inject ozone gas.If silicon wafer surface becomes dry, then can carry out of short duration injection so that the boundary layer liquid film is replenished, this guarantees that the silicon wafer surface that exposes always keeps moistening and silicon wafer surface always keeps high temperature, thereby helps the cleaning of silicon wafer surface.
Make the air pressure of ozone in the airtight process cavity of high-pressure ozone reach 1 more than the atmospheric pressure, the speed that this moment, ozone gas diffused to silicon wafer surface by the boundary layer raises with the increase of ozone air pressure, the air pressure of ozone in the airtight process cavity of high-pressure ozone is remained on for example 3 atmospheric pressure of predetermined pressure, and the air pressure in Pressure gauge indication process cavity continues to inject ozone gas during less than predetermined pressure, to keep the stability of technological parameter in the cleaning process.
Abovementioned steps is carried out after the one or many, also will make silicon wafer experience subsequent step, for example uses steps such as plasma water rinsing, and at this moment, the ozone gas in the process cavity also will be removed with for example nitrogen stream.
Experiment finds, according to the difference of the initial cleannes of silicon wafer surface, utilize sample that the wet cleaning of high pressure cleans obviously can with compare with traditional HydrOzone technology still less number of times or the shorter time remove the pollutant of silicon wafer surface clean.
In addition, if the silicon wafer surface pollutant component is complicated or be difficult to remove, can also in the water that cleans usefulness, add other auxiliary elements such as HF to improve cleansing power.
The method according to this invention is cleaned the 150mm silicon wafer that is coated with 1 micron photoresist.In process cavity, sprayed deionized water steam 10 minutes, thereby process cavity is carried out preheating.In cleaning process, use the stream of pulses of deionized water steam, about 5 seconds kinds of promptly every injection just stop to spray 10 seconds kinds.Wafer rotates with the speed of 800rpm, and with 3 liters/minute speed deionized water steam is ejected in the process cavity.By independent tubes with 8 liters/minute speed with ozone injection in process cavity, the pressure in the process cavity is 1 atmospheric pressure, the cleaning rate of this moment is 7234 /min.
Cleaning identical silicon wafer with the similar process conditions of embodiment 1, but the pressure in the process cavity is 2 atmospheric pressure, and the cleaning rate of this moment is about 14000 /min, is almost 2 times of cleaning rate among the embodiment 1.
The method according to this invention is removed the natural oxide layer of silicon wafer surface.In process cavity, spray 500: 1 the H that is heated to 65 ℃ with 3 liters/minute speed
2O: HF mixture, wafer be with the rotation of the speed of 800rpm, by independent tubes with 8 liters/minute speed with ozone injection in process cavity, the pressure in the process cavity is 1 atmospheric pressure, obtains SiO
2Clearance rate be about 6 /min.
Embodiment 4
Cleaning identical silicon wafer with the similar process conditions of embodiment 3, but the pressure in the process cavity is 2 atmospheric pressure, the SiO of this moment
2Clearance rate be about 12 /min, be 2 times of clearance rate among the embodiment 3.
Industrial usability
The present invention is applicable to and need removes or the various manufacturing steps of selective removal pollutant from surface of the work, is particularly useful for cleaning electronic component member such as semiconductor chip, glass substrate, electronic component and is used to make the parts etc. of the equipment of these parts.
Though specifically illustrate and described the present invention, it should be appreciated by those skilled in the art that and to carry out the various variations on form and the details and can not deviate from the spirit and scope of the present invention the present invention with reference to exemplary embodiment of the present invention.Protection scope of the present invention such as appended claims limit.
Claims (10)
1. high-pressure wet cleaning method is characterized in that wet cleaning process carries out under the condition that has high-pressure ozone gas.
2. according to the high-pressure wet cleaning method of claim 1, may further comprise the steps:
Workpiece to be cleaned is placed the airtight process cavity of high-pressure ozone;
Make described workpiece rotation;
Fluid is incorporated into the surface of rotational workpieces, to form thin boundary layer at surface of the work;
In described process cavity, inject ozone gas, and increase the air pressure of ozone in the described process cavity, make ozone gas diffuse to surface of the work by the boundary layer, thereby with the pollutant oxidation of surface of the work and remove.
3. according to the high-pressure wet cleaning method of claim 1 or 2, wherein said workpiece comprises silicon wafer.
4. according to the high-pressure wet cleaning method of claim 1 or 2, wherein said fluid comprises the water and the hydrofluoric acid of heating or vaporization.
5. according to the high-pressure wet cleaning method of claim 1 or 2, also comprise the step that fluid is heated to 26-200 ℃.
6. according to the high-pressure wet cleaning method of claim 1 or 2, also comprise the step that fluid is heated at least 95 ℃.
7. according to the high-pressure wet cleaning method of claim 1 or 2, also comprise by the rotary speed of adjusting workpiece and/or the step that described flow rate of fluid is controlled boundary layer thickness.
8. according to the high-pressure wet cleaning method of claim 1 or 2, wherein described fluid is ejected into surface of the work.
9. according to the high-pressure wet cleaning method of claim 1 or 2, the ozone that wherein is injected in the described process cavity is dry gas, and the air pressure of ozone is at least 1 atmospheric pressure in the described process cavity.
10. according to the high-pressure wet cleaning method of claim 1 or 2, the ozone that wherein is injected in the described process cavity is dry gas, and the air pressure of ozone is at least 2 atmospheric pressure in the described process cavity.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102446815A (en) * | 2010-10-14 | 2012-05-09 | 中芯国际集成电路制造(上海)有限公司 | Method for forming interconnecting groove and through hole and method for forming interconnecting structure |
| CN102476108A (en) * | 2010-11-23 | 2012-05-30 | 中国科学院微电子研究所 | High-temperature vapor-water mixed jet cleaning system and method |
| CN103100964A (en) * | 2011-11-11 | 2013-05-15 | 中芯国际集成电路制造(上海)有限公司 | Metal grinding protecting device, metal grinding protecting method and chemical machinery grinding system |
| CN104562228A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preventing spinning-solution conveying pipe from crusting |
| CN108039315A (en) * | 2017-12-15 | 2018-05-15 | 浙江晶科能源有限公司 | A kind of cleaning method of silicon chip |
| CN109659229A (en) * | 2017-10-10 | 2019-04-19 | 应用材料公司 | The method for being chemically-mechanicapolish polished (CMP) processing with ozone |
-
2006
- 2006-04-03 CN CN 200610025418 patent/CN101049598A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102446815A (en) * | 2010-10-14 | 2012-05-09 | 中芯国际集成电路制造(上海)有限公司 | Method for forming interconnecting groove and through hole and method for forming interconnecting structure |
| CN102446815B (en) * | 2010-10-14 | 2016-03-16 | 中芯国际集成电路制造(上海)有限公司 | Form the method for interconnection channel and through hole and form the method for interconnection structure |
| CN102476108A (en) * | 2010-11-23 | 2012-05-30 | 中国科学院微电子研究所 | High-temperature vapor-water mixed jet cleaning system and method |
| CN103100964A (en) * | 2011-11-11 | 2013-05-15 | 中芯国际集成电路制造(上海)有限公司 | Metal grinding protecting device, metal grinding protecting method and chemical machinery grinding system |
| CN103100964B (en) * | 2011-11-11 | 2015-11-25 | 中芯国际集成电路制造(上海)有限公司 | Metal grinding protective device and guard method, chemical machinery polishing system |
| CN104562228A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preventing spinning-solution conveying pipe from crusting |
| CN104562228B (en) * | 2013-10-28 | 2017-09-15 | 中国石油化工股份有限公司 | The method for preventing spinning solution delivery pipe skinning |
| CN109659229A (en) * | 2017-10-10 | 2019-04-19 | 应用材料公司 | The method for being chemically-mechanicapolish polished (CMP) processing with ozone |
| CN108039315A (en) * | 2017-12-15 | 2018-05-15 | 浙江晶科能源有限公司 | A kind of cleaning method of silicon chip |
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Open date: 20071010 |