CN105448815B - The cleaning method and semiconductor devices of contact hole - Google Patents
The cleaning method and semiconductor devices of contact hole Download PDFInfo
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- CN105448815B CN105448815B CN201410443811.9A CN201410443811A CN105448815B CN 105448815 B CN105448815 B CN 105448815B CN 201410443811 A CN201410443811 A CN 201410443811A CN 105448815 B CN105448815 B CN 105448815B
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Abstract
This application discloses a kind of cleaning method of contact hole and semiconductor devices.Wherein, which includes the following steps：Contact treatment is carried out to contact hole using containing oxidizing agent solution, to form metal oxide on the surface of metal gates；Using containing H2SO4And H2O2Cleaning reagent contact hole is started the cleaning processing, to remove the etch residue and metal oxide in contact hole.In the cleaning method, the oxidative decomposing section etch residue of energy containing oxidizing agent solution, to remove the partial etching residue in contact hole；Being in direct contact between cleaning reagent and metal gates in subsequent wet processing procedure can be reduced by being formed by metal oxide, be damaged caused by metal gates to reduce cleaning process.Meanwhile cleaning reagent further removes the etch residue in contact hole, to further improve the effect of cleaning contact hole.
Description
Technical field
This application involves the technical fields of semiconductor integrated circuit, in particular to a kind of cleaning method of contact hole
And semiconductor devices.
Background technology
In the manufacturing process of semiconductor devices, needs to form contact hole on metal gates, then fill out in the contact hole
Conductive material is filled to form conductive plunger, so that metal gates are electrically connected by conductive plunger with interconnecting metal layer formation.It is formed
The method of contact hole generally includes following steps：First, substrate is provided, and is formed with grid on substrate and around grid
First medium layer；Then, second dielectric layer is formed on metal gates and first medium layer；Finally, second dielectric layer is etched extremely
Metal gates are exposed, to form contact hole.
In the method for above-mentioned formation contact hole, it is (predominantly organic that etching process can generate etch residue in the contact hole
Polymer, such as residual photoresist or residual etching gas), which can influence between contact hole and conductive plunger
Interlinking reliability, and then influence the performance of semiconductor devices.In order to remove the etch residue in contact hole, it usually needs docking
Contact hole is cleaned.Currently, being cleaned to contact hole by using the cleaning reagent containing organic acid (such as carboxylic acid).However,
The cleaning performance unobvious of the cleaning reagent, and cleaning process can also cause metal gates damage (corrosion metal gates).
To solve the above-mentioned problems, technical staff attempts to reduce the stand-by period (Q between etching process and cleaning process
Time), and the quantity of chip in every batch of cleaning process is reduced, however do not improve significantly cleaning performance.In addition, technology
Personnel also attempt to increase scavenging period, and cleaning performance does not still improve significantly.Therefore, if improving the effect of cleaning contact hole
Fruit, and reduce cleaning process and damaged caused by metal gates, become one of technical barrier urgently to be resolved hurrily.
Invention content
The application is intended to provide a kind of cleaning method and semiconductor devices of contact hole, to improve the effect of cleaning contact hole
Fruit, and reduce cleaning process and damaged caused by metal gates.
To achieve the goals above, this application provides a kind of cleaning methods of contact hole, and the contact hole is by etching position
It is formed in the dielectric layer on metal gates to metal gates are exposed, which includes the following steps：Using containing oxidation
Agent solution carries out contact treatment to contact hole, to form metal oxide on the surface of metal gates；Using containing H2SO4And H2O2
Cleaning reagent contact hole is started the cleaning processing, to remove the etch residue and metal oxide in contact hole.
Further, it is Ozone Water or aqueous hydrogen peroxide solution containing oxidizing agent solution in the step of contact treatment.
Further, O in Ozone Water3Content be 10~80ppm；H in aqueous hydrogen peroxide solution2O2Volume fraction be
20%~50%.
Further, the temperature of contact treatment is 20 DEG C~45 DEG C, and the time of contact treatment is 1~10min.
Further, in the step of cleaning treatment, cleaning reagent H2SO4And H2O2Aqueous solution, wherein H2O、H2SO4With
H2O2Volume ratio be 100：1~5：0.2~2.
Further, in the step of cleaning treatment, cleaning reagent also includes HF, and contents of the HF in cleaning reagent is 5
~20ppm.
Further, the temperature of cleaning treatment is 120 DEG C~150 DEG C, and the time of cleaning treatment is 1~10min.
Further, after the cleaning treatment the step of, cleaning method further includes cleaning contact hole using deionized water
Step.
Further, the material of metal gates is Al.
Present invention also provides a kind of semiconductor devices, including substrate, the metal gates being set on substrate, and setting
In the contact hole on metal gates, wherein the contact hole is handled through above-mentioned cleaning method provided by the present application.
Using the technical solution of the application, the application carries out contact treatment using containing oxidizing agent solution to contact hole first,
To form metal oxide on the surface of metal gates, then using containing H2SO4And H2O2Cleaning reagent contact hole is carried out it is clear
Processing is washed, to remove the etch residue and metal oxide in contact hole.In the contact treatment the step of, contain oxidizing agent solution
Energy oxidative decomposing section etch residue, to remove the partial etching residue in contact hole；It can also oxygen containing oxidizing agent solution
Change metal gates, formed metal oxide can be reduced in subsequent wet processing procedure between cleaning reagent and metal gates
It is in direct contact, is damaged caused by metal gates to reduce cleaning process.In the cleaning treatment the step of, in cleaning reagent
H2SO4It can make etch residue (predominantly organic residue) dehydration and be carbonized, and the H in cleaning reagent2O2Carbonization can be produced
Object is oxidized to carbon monoxide or carbon dioxide gas, to further remove the etch residue in contact hole, and further carries
The high effect of cleaning contact hole.
Description of the drawings
The accompanying drawings which form a part of this application are used for providing further understanding of the present application, and the application's shows
Meaning property embodiment and its explanation do not constitute the improper restriction to the application for explaining the application.In the accompanying drawings：
Fig. 1 shows the flow diagram of the cleaning method for the contact hole that the application embodiment is provided.
Specific implementation mode
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.The application is described in detail below with reference to the accompanying drawings and in conjunction with the embodiments.
It should be noted that term used herein above is merely to describe specific implementation mode, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singulative
Be also intended to include plural form, additionally, it should be understood that, when in the present specification using belong to "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or combination thereof.
For ease of description, herein can with use space relative terms, as " ... on ", " ... on
Side ", " ... upper surface ", " above " etc., for describing such as a device shown in the figure or feature and other devices
The spatial relation of part or feature.It should be understood that spatially relative term is intended to comprising in addition to device is described in figure
Orientation except different direction in use or operation.For example, if the device in attached drawing is squeezed, be described as "
To be positioned as after other devices or construction top " or the device of " on other devices or construction " " in other devices or
Construction lower section " or " under other devices or construction ".Thus, exemplary term " on the top " may include
Two kinds of orientation of " on the top " and " below ".The device can also other different modes positioning (be rotated by 90 °
Or it is in other orientation), and respective explanations are made to the opposite description in space used herein above.
As described in background technology, the cleaning performance unobvious of the method for existing cleaning contact hole, and cleaned
Journey can also cause to damage to metal gates.Present inventor studies regarding to the issue above, proposes a kind of contact hole
Cleaning method.Wherein, the contact hole is by etching dielectric layer on metal gates to being formed by exposing metal gates.Such as
Shown in Fig. 1, which includes the following steps：Contact treatment is carried out to contact hole using containing oxidizing agent solution, in metal
The surface of grid forms metal oxide；Using containing H2SO4And H2O2Cleaning reagent contact hole is started the cleaning processing, to go
Except etch residue and metal oxide in contact hole.
In the contact treatment the step of, the oxidative decomposing section etch residue of energy containing oxidizing agent solution, to remove contact
Part etch residue in hole；Containing oxidizing agent solution can also oxidized metal grid, formed metal oxide can reduce subsequently
Being in direct contact between wet-treating Cleaning Process reagent and metal gates makes metal gates to reduce cleaning process
At damage.In the cleaning treatment the step of, H in cleaning reagent2SO4It can make etch residue (predominantly organic residue)
It is dehydrated and is carbonized, and H in cleaning reagent2O2Carbonized product can be oxidized to carbon monoxide or carbon dioxide gas, to further
The etch residue in contact hole is removed, and further improves the effect of cleaning contact hole.
The illustrative embodiments according to the application are described in more detail below.However, these illustrative embodiments
It can be implemented by many different forms, and should not be construed to be limited solely to embodiments set forth herein.It should
These embodiments that are to provide understood are in order to enable disclosure herein is thoroughly and complete, and by these exemplary realities
The design for applying mode is fully conveyed to those of ordinary skill in the art.
First, contact treatment is carried out to contact hole using containing oxidizing agent solution, to form metal on the surface of metal gates
Oxide.Wherein, refer to the solution for having higher oxidisability containing oxidizing agent solution, metal gates surface oxidation can be formed
Metal oxide.The material of metal gates can be to be commonly used in the metal of grid, such as Al or Cu.Those skilled in the art
Member can select the component containing oxidizing agent solution according to teachings of the present application, in a preferred embodiment, contain oxidant
Solution is Ozone Water or aqueous hydrogen peroxide solution.O in Ozone Water3Reduction reaction can occur, generate very vivaciously, with strong oxygen
The antozone of change effect, to oxygenolysis organic matter (i.e. etch residue).Aqueous hydrogen peroxide solution also has organic matter
Very strong oxidation, oxidation are slightly below Ozone Water.Certainly, it can also be to also have other oxidants to contain oxidizing agent solution
Solution, be not restricted to above-mentioned preferred embodiment.
In the above-mentioned contact treatment the step of, the concentration of Ozone Water can be set according to actual process demand.It is preferred that
Ground, O in Ozone Water3Content be 10~80ppm；H in aqueous hydrogen peroxide solution2O2Volume fraction be 20%~50%.Using
Ozone Water and aqueous hydrogen peroxide solution with above-mentioned concentration can more thoroughly remove the etch residue in contact hole, to
Further improve the effect of cleaning contact hole.
When the Ozone Water or aqueous hydrogen peroxide solution provided using above-mentioned preferred embodiment handles contact hole, contact treatment
Temperature, time and the way of contact can be set according to actual process demand.Preferably, the temperature of contact treatment is 20
DEG C~45 DEG C, the time of contact treatment is 1~10min.The mode of contact treatment can be infusion method and rotary spray method.When
So, other than the above-mentioned way of contact, other ways of contact can also be used, those skilled in the art can be according to production practices
Specific requirement and select the suitable way of contact.
For the step of above-mentioned contact treatment is expanded on further and mechanism, below to the mode of contact treatment (infusion method and
Rotary spray method) it is further explained explanation.Infusion method is exactly to be soaked by cleaning solution and the etch residue in contact hole
Chemical reaction and dissolution occur during bubble to achieve the purpose that remove etch residue in contact hole.Simple solution leaching
Its efficiency of bubble method is often unsatisfactory, is arranged so being aided with the physics such as heating, ultrasound, stirring toward contact while using impregnating
It applies.Rotary spray method dissolves the etching residue in contact hole using dissolving (or chemical reaction) effect of sprayed cleaning reagent
Object, while high-speed rotating centrifugal action is utilized, so that the liquid dissolved with impurity is disengaged hole, the liquid in such contact hole in time
Body always keeps very high purity.Simultaneously because sprayed cleaning reagent and the contact hole of rotation have higher relative velocity, so
Larger impact force is will produce to achieve the purpose that remove adsorbing contaminant.
Specifically, include using the step of infusion method progress contact treatment：Oxidizing agent solution will be contained to be placed in rinse bath, controlled
In rinse bath processed then the chip containing contact hole is placed in containing oxidizing agent solution by the temperature containing oxidizing agent solution at 20 DEG C~45 DEG C
The time of middle carry out immersion treatment, immersion treatment is 1~10min.Include by the step of rotary spray method progress contact treatment：
By solution spraying containing oxidant to the chip containing contact hole on, and by low speed rotation (<500rpm) make equal containing oxidizing agent solution
Even distribution in the contact hole, carries out contact treatment under the conditions of temperature is at 20 DEG C~45 DEG C, and time of contact treatment is 1~
10min。
It completes to carry out contact treatment to contact hole using containing oxidizing agent solution, to form metal oxygen on the surface of metal gates
After the step of compound, using containing H2SO4And H2O2Cleaning reagent contact hole is started the cleaning processing, to remove in contact hole
Etch residue and metal oxide.Etch residue in above-mentioned contact through hole predominantly contains Si, C, F, and O's, N is organic residual
Stay object.During cleaning treatment, the H in cleaning reagent2SO4For making the residual organic matter containing C, F, O, N be dehydrated and carbon
Change, and the H in cleaning reagent2O2It is logical to remove contact for carbonized product to be oxidized to carbon monoxide or carbon dioxide gas
Organic residue in hole.
Wherein, above-mentioned to contain H2SO4And H2O2Cleaning reagent refer in cleaning reagent include at least H2SO4And H2O2, can also
Including other components.Preferably, cleaning reagent includes also HF, and cleaning reagent is by H at this time2SO4、H2O2It is formed with HF.HF can be gone
Except the metal oxide layer and etch residue in contact hole, to further improve the effect of cleaning contact hole.
In the above-mentioned cleaning treatment the step of, the concentration of each component can be carried out according to actual process demand in cleaning reagent
Setting.When cleaning reagent is H2SO4And H2O2Aqueous solution when, H2O、H2SO4And H2O2Volume ratio be preferably 100：1~5：0.2
~2.When cleaning reagent includes also HF, contents of the HF in cleaning reagent is preferably 5~20ppm.Using with above-mentioned concentration
Cleaning reagent can more thoroughly remove etch residue in contact hole, to further improve cleaning contact hole effect
Fruit.
When the cleaning reagent provided using above-mentioned preferred embodiment starts the cleaning processing contact hole, the temperature of cleaning treatment
Degree, time and the way of contact can be set according to actual process demand.Preferably, further, the temperature of cleaning treatment
Degree is 120 DEG C~150 DEG C, and the time of cleaning treatment is 1~10min.The mode of cleaning treatment can be infusion method and rotation spray
Leaching method.Certainly, other than above-mentioned cleaning way, other cleaning ways can also be used, those skilled in the art can be according to life
It produces the specific requirement of practice and selects suitable cleaning way.
Specifically, the step of being started the cleaning processing using infusion method include：Cleaning reagent is placed in rinse bath, control is clear
In washing trough then the chip containing contact hole is placed in cleaning reagent and cleans at 120 DEG C~150 DEG C by the temperature of cleaning reagent
The time of processing, cleaning treatment is 1~10min.Include by the step of rotary spray method progress contact treatment：By cleaning reagent
Spray on the chip containing contact hole, and by low speed rotation (<500rpm) make cleaning reagent be uniformly distributed in the contact hole,
Temperature starts the cleaning processing under the conditions of 120 DEG C~150 DEG C, and the time of cleaning treatment is 1~10min.
After the above-mentioned cleaning treatment the step of, deionized water can also be used to clean contact hole, for rinsing contact hole
In particle, such as etch residue, carbonized product, remaining sulfuric acid and hydrogen peroxide etc..Contact hole is cleaned using deionized water
Time and temperature etc. can be with the parameter prior art, details are not described herein.
Present invention also provides a kind of semiconductor devices, including substrate, the metal gates being set on substrate, and setting
In the contact hole on metal gates, wherein the contact hole is handled through above-mentioned cleaning method provided by the present application.The semiconductor
Etch residue is removed in device, to improve the performance of semiconductor devices.Certainly, which further includes setting
The devices such as the conductive plunger in contact hole are placed in, concrete structure can be with the parameter prior art, and details are not described herein.
The cleaning method of contact hole provided by the present application is further illustrated below in conjunction with embodiment.
Embodiment 1
A kind of cleaning method of contact hole is present embodiments provided, is included the following steps：
Using Ozone Water (wherein O3Content be 60ppm) to contact hole carry out contact treatment, specifically include following steps：
Ozone Water is placed in rinse bath, the temperature of Ozone Water in rinse bath is controlled at 25 DEG C, is then placed in the chip containing contact hole
Immersion treatment is carried out in Ozone Water, the time of immersion treatment is 10min；
Using by H2SO4And H2O2Cleaning reagent (the H of composition2O、H2SO4And H2O2Volume ratio be preferably 100：1：0.2)
Contact hole is started the cleaning processing, following steps are specifically included：Cleaning reagent is placed in rinse bath, controls and is cleaned in rinse bath
Then chip containing contact hole is placed in cleaning reagent and starts the cleaning processing at 120 DEG C by the temperature of reagent, cleaning treatment when
Between be 10min.
Comparative example 1
A kind of cleaning method of contact hole is present embodiments provided, is included the following steps：
Cleaning reagent (product type Reiz38, main component are organic carboxyl acid) is used to carry out at cleaning contact hole
Reason, specifically includes following steps：Cleaning reagent is placed in rinse bath, control rinse bath in cleaning reagent temperature at 100 DEG C,
Then the chip containing contact hole is placed in cleaning reagent and is started the cleaning processing, the time of cleaning treatment is 15min.
The microscopic appearance in embodiment 1 and comparative example 1 before and after cleaning contact hole is observed by SEM, and using the side of statistics
Method calculates etch residue removal rate in contact hole.The result shows that etch residue removes in the contact hole that comparative example 1 obtains
Rate is only 62%, and Al gate surfaces generate higher losses, and waste isAnd etch residue is gone in the embodiment of the present application 1
Except rate is up to 91%, and Al gate surface wastes are onlyIt is provided using the application it can be seen from above-mentioned data analysis
Technical solution so that etch residue is significantly reduced in contact hole.
It can be seen from the above description that the application the above embodiments realize following technique effect：
(1) in the contact treatment the step of, the oxidative decomposing section etch residue of energy containing oxidizing agent solution, to which removal connects
Partial etching residue in contact hole；Containing oxidizing agent solution can also oxidized metal grid, formed metal oxide can reduce
Being in direct contact between cleaning reagent and metal gates in subsequent wet processing procedure, to reduce cleaning process to metal gate
Damage caused by pole.
(2) in the cleaning treatment the step of, H in cleaning reagent2SO4It can make etch residue (predominantly organic residue
Object) it is dehydrated and is carbonized, and H in cleaning reagent2O2Carbonized product can be oxidized to carbon monoxide or carbon dioxide gas, thus into
One step removes etch residue in contact hole, and further improves the effect of cleaning contact hole.
The foregoing is merely the preferred embodiments of the application, are not intended to limit this application, for the skill of this field
For art personnel, the application can have various modifications and variations.Within the spirit and principles of this application, any made by repair
Change, equivalent replacement, improvement etc., should be included within the protection domain of the application.
Claims (10)
1. a kind of cleaning method of contact hole, the contact hole is located at the dielectric layer on metal gates to exposing by etching
It states metal gates and is formed, which is characterized in that the cleaning method includes the following steps：
Contact treatment is carried out to the contact hole using containing oxidizing agent solution, to form metal oxygen on the surface of the metal gates
Compound；
Using containing H2SO4And H2O2Cleaning reagent the contact hole is started the cleaning processing, to remove the quarter in the contact hole
Lose residue and the metal oxide.
2. cleaning method according to claim 1, which is characterized in that described containing oxidation in the step of the contact treatment
Agent solution is Ozone Water or aqueous hydrogen peroxide solution.
3. cleaning method according to claim 2, which is characterized in that O in the Ozone Water3Content be 10~80ppm；
H in the aqueous hydrogen peroxide solution2O2Volume fraction be 20%~50%.
4. cleaning method according to claim 3, which is characterized in that the temperature of the contact treatment is 20 DEG C~45 DEG C,
The time of the contact treatment is 1~10min.
5. cleaning method according to claim 1, which is characterized in that in the step of the cleaning treatment, the cleaning examination
Agent is H2SO4And H2O2Aqueous solution, wherein H2O、H2SO4And H2O2Volume ratio be 100：1~5：0.2~2.
6. cleaning method according to claim 5, which is characterized in that in the step of the cleaning treatment, the cleaning examination
Agent also includes HF, and contents of the HF in the cleaning reagent is 5~20ppm.
7. cleaning method according to claim 5 or 6, which is characterized in that the temperature of the cleaning treatment be 120 DEG C~
150 DEG C, the time of the cleaning treatment is 1~10min.
8. cleaning method according to claim 1, which is characterized in that described clear after the cleaning treatment the step of
Washing method further includes the steps that cleaning the contact hole using deionized water.
9. cleaning method according to claim 1, which is characterized in that the material of the metal gates is Al.
10. a kind of semiconductor devices, including substrate, the metal gates being set on the substrate, and it is set to the metal
Contact hole on grid, which is characterized in that the contact hole is handled through the cleaning method described in any one of claim 1 to 9
It forms.
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| CN201410443811.9A CN105448815B (en) | 2014-09-02 | 2014-09-02 | The cleaning method and semiconductor devices of contact hole |
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| CN201410443811.9A CN105448815B (en) | 2014-09-02 | 2014-09-02 | The cleaning method and semiconductor devices of contact hole |
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| CN105448815B true CN105448815B (en) | 2018-09-18 |
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| CN106653562A (en) * | 2015-11-03 | 2017-05-10 | 中芯国际集成电路制造(上海)有限公司 | Method of cleaning contact hole |
| CN109148490B (en) * | 2018-10-15 | 2021-04-27 | 深圳市华星光电半导体显示技术有限公司 | Array substrate, manufacturing method thereof and liquid crystal display panel |
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| CN1591819A (en) * | 2003-09-04 | 2005-03-09 | 南亚科技股份有限公司 | Method internal connector producing process and metal silicide layer removing method |
| CN101303987A (en) * | 2007-05-11 | 2008-11-12 | 中芯国际集成电路制造(上海)有限公司 | Method for manufacturing semiconductor device |
| CN102543683A (en) * | 2010-12-30 | 2012-07-04 | 中芯国际集成电路制造(上海)有限公司 | Reprocessing method for photoetching process |
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| JPWO2014057861A1 (en) * | 2012-10-11 | 2016-09-05 | セントラル硝子株式会社 | Glass substrate cleaning method |
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|---|---|---|---|---|
| CN1591819A (en) * | 2003-09-04 | 2005-03-09 | 南亚科技股份有限公司 | Method internal connector producing process and metal silicide layer removing method |
| CN101303987A (en) * | 2007-05-11 | 2008-11-12 | 中芯国际集成电路制造(上海)有限公司 | Method for manufacturing semiconductor device |
| CN102543683A (en) * | 2010-12-30 | 2012-07-04 | 中芯国际集成电路制造(上海)有限公司 | Reprocessing method for photoetching process |
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