CN105575762A - Method for eliminating wafer surface defect in wet etching - Google Patents

Method for eliminating wafer surface defect in wet etching Download PDF

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Publication number
CN105575762A
CN105575762A CN201410541481.7A CN201410541481A CN105575762A CN 105575762 A CN105575762 A CN 105575762A CN 201410541481 A CN201410541481 A CN 201410541481A CN 105575762 A CN105575762 A CN 105575762A
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Prior art keywords
phosphoric acid
wafer
silicon nitride
silicon dioxide
wet etching
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CN201410541481.7A
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CN105575762B (en
Inventor
胡春周
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Semiconductor Manufacturing International Shanghai Corp
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Semiconductor Manufacturing International Shanghai Corp
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Abstract

The invention provides a method for eliminating a wafer surface defect in wet etching. A control wafer is used for replacing a processing wafer to manufacture a proper silicide-contained phosphoric acid solution, thereby reducing the production cost. A silicon nitride film of the control wafer reacts with the phosphoric acid solution to generate the silicide for inhibiting silicon dioxide corrosion, so that a problem of sound filed cost increasing because of adding the silicide into the phosphoric acid solution independently can be effectively solved. Impurities attached to the surface of the control wafer after silicon nitride corrosion are removed by using a mixed solution with phosphoric acid and sulfuric acid in a proper ratio; and impurities on the surface of the processing wafer are also removed by using a mixed solution with phosphoric acid and sulfuric acid in a same proper ratio, so that the product yield is effectively reduced under the circumstance that no defect exist on the wafer surface.

Description

The method of wafer surface defects is removed in a kind of wet etching
Technical field
The present invention relates to a kind of semiconductor manufacturing process, particularly relate to a kind of method removing wafer surface defects in wet etching.
Background technology
Silicon nitride is a kind of dielectric material be widely used in silicon wafer process.Silicon nitride film is formed on a semiconductor substrate typically, and the general barrier layer being used as silicon dioxide in etching wafer, is formed at the upper surface of silicon dioxide layer.And in wet-etching technology process, usually etch with phosphoric acid or corrode this silicon nitride barrier.In the process of corrosion, normally numerous wafer is placed in phosphoric acid solution simultaneously, owing to being in silicon nitride in phosphoric acid solution and silicon dioxide has different etch rates (etching selection ratio), namely in the same time, phosphoric acid corrosion silicon nitride is different with the speed of silicon dioxide.
The factor affecting silicon nitride and the etching selection ratio of silicon dioxide in phosphoric acid has the temperature of soak time, phosphoric acid solution and the groove life etc. of etching reaction groove usually; If it is improper that these influencing factors are grasped, likely cause and also corrosion is caused to silicon dioxide while corroding silicon nitride, therefore just define the defect of wafer.
When increasing containing the silicon concentration in the etching groove of phosphoric acid, the etch rate of silicon dioxide can reduce.While corroding silicon nitride, corrosion not being formed to silicon dioxide in order to making at present, usually in phosphoric acid solution, adding the material such as silica flour or silicide suppress to silicon dioxide formation corrosion.The method causes the rising of manufacturing cost on the one hand; The impurities adhere such as the silicide formed after corroding silicon nitride on the other hand and oxide can cause defect to wafer further on the surface of wafer.
The method that another reduction silicon dioxide is corroded is the number as far as possible controlling wafer in etching groove, has to like this reduce the efficiency of producing.
Therefore, to be necessary to propose in a kind of new wet etching, for removing the method for wafer surface defects, to solve the problems referred to above.
Summary of the invention
The shortcoming of prior art in view of the above, the object of the present invention is to provide a kind of method removing wafer surface defects in wet etching, the impurity formed after being etched for solving in prior art the cost increase, the silicon nitride that to add silicon matter in addition and cause in phosphoric acid solution easily causes defect to wafer and has to reduce the problem of production efficiency for reducing wafer defect.
For achieving the above object and other relevant objects, the invention provides a kind of method removing wafer surface defects in wet etching, the method at least comprises: (1) provides some control wafers containing silicon dioxide and silicon nitride film; (2) described control wafer is dipped in the first etching tank containing phosphoric acid solution; (3) regulate soak time that the silicon nitride film in described control wafer is completely dissolved; The silicon nitride being dissolved in phosphoric acid forms silicide to suppress phosphoric acid to the corrosion of silicon dioxide in described first etching tank; (4) some processing procedure wafers containing silicon dioxide and silicon nitride film are placed in the first etching tank processed through step (3) silicon nitride film is removed; (5) the second etching tank containing phosphoric acid and sulfuric acid solution is provided; (6) proportioning of phosphoric acid and sulfuric acid in described second etching tank is regulated to make the etching selection ratio of silicon nitride to silicon dioxide the highest; (7) the described processing procedure wafer in step (4) to be placed in the phosphoric acid of step (6) identical proportioning and sulfuric acid solution to remove the impurity of described processing procedure crystal column surface, to obtain flawless processing procedure wafer.
As a kind of preferred version of method removing wafer surface defects in wet etching of the present invention, in described step (2), in the first etching tank, the temperature of phosphoric acid solution is 150 DEG C ~ 160 DEG C.
As a kind of preferred version of method removing wafer surface defects in wet etching of the present invention, in described step (1), the number of control wafer is 100 ~ 200.
As a kind of preferred version of method removing wafer surface defects in wet etching of the present invention, the soak time in described step (3) is 20 minutes ~ 60 minutes.
As a kind of preferred version of method removing wafer surface defects in wet etching of the present invention, in phosphoric acid solution described in described step (3), the concentration of silicon is 30ppm ~ 50ppm.
As a kind of preferred version of method removing wafer surface defects in wet etching of the present invention, only containing a kind of solution of phosphoric acid in described first etching tank in described step (2); Only containing the mixed solution be made up of phosphoric acid and sulfuric acid in described second etching tank in described step (6).
As a kind of preferred version of method removing wafer surface defects in wet etching of the present invention, the processing procedure number of wafers in described step (4) is not more than the control wafer number in described step (1).
As a kind of preferred version of method removing wafer surface defects in wet etching of the present invention, the processing procedure number of wafers in described step (4) is identical with the control wafer number in described step (1).
As a kind of preferred version of method removing wafer surface defects in wet etching of the present invention, the mass concentration of the phosphoric acid in described step (6) in the second etching tank is 20% ~ 40%.
As a kind of preferred version of method removing wafer surface defects in wet etching of the present invention, the situation that in described step (6), silicon nitride is the highest to the etching selection ratio of silicon dioxide is: silicon nitride is corroded completely, and silicon dioxide is not corroded completely.
As mentioned above, in wet etching of the present invention, remove the method for wafer surface defects, there is following beneficial effect: the phosphoric acid solution containing silicide adopting control wafer to replace processing procedure wafer manufacturing suitable, reduces production cost; The silicon nitride film that control wafer carries and phosphatase reaction generate the silicide for suppressing silicon dioxide etching, effectively prevent and in phosphoric acid, add due to independent the problem that silicide causes sound field cost increase; The phosphoric acid of suitable proportioning and the mixed solution of sulfuric acid is adopted to remove in control wafer after silicon nitride etch at the impurity that crystal column surface adheres to, remove processing procedure crystal column surface impurity with the mixed solution of the phosphoric acid of identical proportioning and sulfuric acid, under making the flawless situation of crystal column surface, effectively reduce the yield of product.
Accompanying drawing explanation
Fig. 1 is shown as the schematic flow sheet of the method removing wafer surface defects in wet etching of the present invention.
Fig. 2 ~ Fig. 5 is shown as the operation schematic diagram of each step of the present invention.
Element numbers explanation
S1 ~ S7 step
20 first etching tanks
201 control wafers
202 phosphoric acid solutions
203 silicides
204 processing procedure wafers
21 second etching tanks
The mixed solution of 205 phosphoric acid and sulfuric acid
Embodiment
Below by way of specific instantiation, embodiments of the present invention are described, those skilled in the art the content disclosed by this specification can understand other advantages of the present invention and effect easily.The present invention can also be implemented or be applied by embodiments different in addition, and the every details in this specification also can based on different viewpoints and application, carries out various modification or change not deviating under spirit of the present invention.
Refer to Fig. 1.It should be noted that, the diagram provided in the present embodiment only illustrates basic conception of the present invention in a schematic way, then only the assembly relevant with the present invention is shown in graphic but not component count, shape and size when implementing according to reality is drawn, it is actual when implementing, and the kenel of each assembly, quantity and ratio can be a kind of change arbitrarily, and its assembly layout kenel also may be more complicated.
As shown in Figure 1, the schematic flow sheet of the method for removing wafer surface defects in wet etching of the present invention that what Fig. 1 represented is; Step (1): some control wafers containing silicon dioxide and silicon nitride film are provided; In semiconductor production process, the Main Function of described control wafer is stability and the repeatability of monitoring board.Or be used for carrying out the experiment of certain road technique, then test the performance of control wafer.Therefore, control wafer be not really for the production of wafer, be not namely processing procedure wafer.Control wafer in the present invention contains silicon dioxide layer and silicon nitride film, and described silicon nitride film is generally formed at the upper surface of described silicon dioxide, the general barrier layer being used as etching.In the present invention, etching is formed at the mode of the silicon nitride of described silicon dioxide upper surface is wet etching or wet etching.Then implementation step (2): described control wafer is dipped in the first etching tank containing phosphoric acid solution; As shown in Figure 2, the object of the first etching tank 20 in this step be placed in described control wafer 201 containing phosphoric acid solution 202 is eroded by described silicon nitride film; And generally, after immersion reaches certain hour, phosphoric acid all can form corrosion to silicon nitride film and silicon dioxide, and in corrosion process, the temperature of phosphoric acid solution also can form different etching selection ratio to silicon nitride and silicon dioxide, and namely phosphoric acid is different to the corrosion rate both this.In order to make the etching selection ratio of silicon nitride to silicon dioxide the highest, preferably, only containing a kind of solution of phosphoric acid in described first etching tank 20, although, other acid solutions also can form corrosion to silicon nitride, but in order to ensure that silicon nitride is stablized the Selection radio that silicon dioxide etches, in described first etching tank in the present embodiment, only have a kind of solution of phosphoric acid.
Implementation step (3): as shown in Figure 3, regulates soak time that the silicon nitride film in described control wafer 201 is completely dissolved; Namely silicon nitride film in the control wafer 201 in described phosphoric acid solution 202 is soaked in by phosphoric acid corrosion; The silicon nitride being dissolved in phosphoric acid forms silicide 203 to suppress phosphoric acid to the corrosion of silicon dioxide in described first etching tank 20; Because phosphoric acid all has corrosivity to silicon nitride and silicon dioxide, the object of this step is the corrosion that protection silicon dioxide avoids by phosphoric acid, and need to remove the silicon nitride film being positioned at silicon dioxide upper surface, and in phosphoric acid solution, the silicide that silicon nitride and phosphatase reaction are formed is inhibited to phosphoric acid corrosion silicon dioxide, therefore, as long as regulate soak time just can reach above-mentioned effect, as a preferred embodiment of the present invention, described soak time is 20 minutes ~ 60 minutes; In this time range, silicon nitride is corroded completely and phosphoric acid can not form corrosion to silicon dioxide.Equally, the temperature of the phosphoric acid solution in the first etching tank also affects the etching selection ratio of silicon nitride to silicon dioxide, and therefore, preferably, in described first etching tank of the present invention, the temperature of phosphoric acid solution is 150 DEG C ~ 160 DEG C.In this temperature range, in phosphoric acid solution, the etching selection ratio of silicon nitride to silicon dioxide is the highest.
Experiment according to prior art proves, due to the disposable control wafer number be soaked in phosphoric acid solution decide produce silicide 203 number, when said temperature and soak time certain, this is stronger to the inhibitory action of silicon dioxide etching more at most for described silicide 203, therefore, in order to make not form corrosion to silicon dioxide as far as possible, the number of the control wafer be soaked in described first etching tank in described step (1) is 100 ~ 200 in the present embodiment preferably.
When above-mentioned soak time and corrosion temperature certain, another kind of preferred version of the present invention is the concentration of silicon in described silicide 203 is 30ppm ~ 50ppm.In this concentration range, the etching selection ratio of described silicon nitride to silicon dioxide is the highest.
Then implementation step (4): some processing procedure wafers containing silicon dioxide and silicon nitride film are placed in the first etching tank processed through step (3) silicon nitride film is removed; As shown in Figure 4, described processing procedure wafer 204 refer to really for the production of in carry out the wafer produced in batches.The quality of described processing procedure wafer 204 etching effect in this etching technics directly affects the performance of this processing procedure wafer and the yield of product.Usual described processing procedure wafer 204 is by after some technical process in production, the silicon nitride film as barrier layer can be formed on silica, and containing the silicide that silicon nitride and phosphatase reaction produce in the phosphoric acid solution of process in step (3), the object of the phosphoric acid solution containing silicide that described step (4) prepares before being placed in by the described processing procedure wafer containing silicon dioxide and silicon nitride film utilizes phosphoric acid to the corrosiveness of silicon nitride, and the inhibitory action utilizing the silicide in described phosphoric acid to be corroded to silicon dioxide further, only corrosion is formed to the barrier layer silicon nitride in described processing procedure wafer, corrosion is not formed to silicon dioxide, if the silicon dioxide in processing procedure wafer is corroded, then this processing procedure wafer then likely can produce defect, affect the yield of final products.
What suppress the silicon dioxide in corrosion processing procedure wafer to utilize in this step is the silicide that in control wafer, silicon nitride and phosphatase reaction produce, and avoids and in phosphoric acid solution, adds silicide in addition and cause cost increase.In this step, after the silicon nitride on processing procedure wafer has been corroded, no longer need to regulate soak time, because containing silicide in described first etching tank, define suppression to the corrosion of silicon dioxide, therefore how long soak time all can not make silicon dioxide be corroded.
In order to described silicide can be made best to the inhibitory action of silicon dioxide etching in this step, the number of usually selected processing procedure wafer should be not more than the number of control wafer in described step (1), therefore, be corroded to not affect again silicon dioxide in described processing procedure wafer while of reaching higher production efficiency, preferably, the number of processing procedure wafer described in this step is identical with the number of control wafer in described step (1).
Implementation step (5): the second etching tank containing phosphoric acid and sulfuric acid solution is provided; As shown in Figure 5, the mixed solution 205 of phosphoric acid and sulfuric acid is contained in described second etching tank 21.
Then implementation step (6): regulate the proportioning of phosphoric acid and sulfuric acid in described second etching tank 21 to make the etching selection ratio of silicon nitride to silicon dioxide the highest; The mixed solution of phosphoric acid and sulfuric acid is used all to have corrosivity to the silicon nitride in processing procedure wafer and silicon dioxide in this step, therefore, in order to make the corrosivity of silicon dioxide minimum, need the proportioning of sulfuric acid and phosphoric acid in the mixed solution 205 of phosphoric acid and sulfuric acid in described second etching tank 21 of adjustment.As a preferred embodiment of the present invention, only containing the mixed solution be made up of phosphoric acid and sulfuric acid in described second etching tank 21 in this step.Further preferably, regulate the proportioning of phosphoric acid and sulfuric acid in described second etching tank 21 to make the mass concentration of phosphoric acid be 20% ~ 40%, under this concentration, the etching selection ratio of silicon nitride to silicon dioxide is the highest.
When silicon nitride is the highest to the etching selection ratio of silicon dioxide, the silicon dioxide in described processing procedure wafer also may be corroded a part, and just the speed of the speed ratio corroding silicon nitride of corrode silicon dioxide is slow; In this embodiment of the present invention, preferably, when in step (6), silicon nitride is the highest to the etching selection ratio of silicon dioxide, silicon nitride is corroded completely, and silicon dioxide is not corroded completely.Described step (6) can continue to test in described containing in the solution of phosphoric acid and sulfuric acid by the control wafer in step (1), makes the etching selection ratio of silicon nitride to silicon dioxide the highest.
Then implementation step (7): the described processing procedure wafer in step (4) to be placed in the phosphoric acid of step (6) identical proportioning and sulfuric acid solution to remove the impurity of described processing procedure crystal column surface, to obtain flawless processing procedure wafer.In the present embodiment, through step (4) process after number identical with described control wafer processing procedure wafer on silicon nitride film removed by described silicide, and in the process removing described silicon nitride, described processing procedure wafer is placed in the phosphoric acid solution containing a large amount of silicide, and described silicide belongs to deposit in phosphoric acid solution, after described processing procedure wafer takes out described first etching tank, the surface of described processing procedure wafer can adhere to a lot of impurity (comprising silicide), if these impurity of processing procedure crystal column surface, the defect of crystal column surface then can be caused further in subsequent production, therefore, in the present invention through step (4) process after processing procedure wafer need be placed into in the phosphoric acid of identical proportioning in described step (6) and sulfuric acid solution to remove the impurity of described processing procedure crystal column surface, obtain flawless processing procedure wafer.
So far whole implementation step of the present invention completes.Remove the method for wafer surface defects in wet etching of the present invention, there are following three beneficial effects: the phosphoric acid solution containing silicide that () adopts control wafer to replace processing procedure wafer manufacturing suitable, reduce production cost; (2) silicon nitride film that carries of control wafer and phosphatase reaction generate the silicide for suppressing silicon dioxide etching, effectively prevent and in phosphoric acid, add due to independent the problem that silicide causes sound field cost increase; (3) phosphoric acid of suitable proportioning and the mixed solution of sulfuric acid is adopted to remove in control wafer after silicon nitride etch at the impurity that crystal column surface adheres to, remove processing procedure crystal column surface impurity with the mixed solution of the phosphoric acid of identical proportioning and sulfuric acid, under making the flawless situation of crystal column surface, effectively reduce the yield of product.
In sum, remove the method for wafer surface defects in wet etching of the present invention, to solve in prior art the impurity that the cost increase, the silicon nitride that to add silicon matter in addition and cause in phosphoric acid solution formed after being etched and easily defect caused to wafer and have to reduce the problem of production efficiency for reducing wafer defect.So the present invention effectively overcomes various shortcoming of the prior art and tool high industrial utilization.
Above-described embodiment is illustrative principle of the present invention and effect thereof only, but not for limiting the present invention.Any person skilled in the art scholar all without prejudice under spirit of the present invention and category, can modify above-described embodiment or changes.Therefore, such as have in art usually know the knowledgeable do not depart from complete under disclosed spirit and technological thought all equivalence modify or change, must be contained by claim of the present invention.

Claims (10)

1. remove a method for wafer surface defects in wet etching, it is characterized in that, the method at least comprises:
(1) some control wafers containing silicon dioxide and silicon nitride film are provided;
(2) described control wafer is dipped in the first etching tank containing phosphoric acid solution;
(3) regulate soak time that the silicon nitride film in described control wafer is completely dissolved; The silicon nitride being dissolved in phosphoric acid forms silicide to suppress phosphoric acid to the corrosion of silicon dioxide in described first etching tank;
(4) some processing procedure wafers containing silicon dioxide and silicon nitride film are placed in the first etching tank processed through step (3) silicon nitride film is removed;
(5) the second etching tank containing phosphoric acid and sulfuric acid solution is provided;
(6) proportioning of phosphoric acid and sulfuric acid in described second etching tank is regulated to make the etching selection ratio of silicon nitride to silicon dioxide the highest;
(7) the described processing procedure wafer in step (4) to be placed in the phosphoric acid of step (6) identical proportioning and sulfuric acid solution to remove the impurity of described processing procedure crystal column surface, to obtain flawless processing procedure wafer.
2. remove the method for wafer surface defects in wet etching according to claim 1, it is characterized in that: in described step (2), in the first etching tank, the temperature of phosphoric acid solution is 150 DEG C ~ 160 DEG C.
3. remove the method for wafer surface defects in wet etching according to claim 1, it is characterized in that: in described step (1), the number of control wafer is 100 ~ 200.
4. remove the method for wafer surface defects in wet etching according to claim 3, it is characterized in that: the soak time in described step (3) is 20 minutes ~ 60 minutes.
5. remove the method for wafer surface defects in wet etching according to claim 1, it is characterized in that: in phosphoric acid solution described in described step (3), the concentration of silicon is 30ppm ~ 50ppm.
6. remove the method for wafer surface defects in wet etching according to claim 1, it is characterized in that: only containing a kind of solution of phosphoric acid in described first etching tank in described step (2); Only containing the mixed solution be made up of phosphoric acid and sulfuric acid in described second etching tank in described step (6).
7. remove the method for wafer surface defects in wet etching according to claim 1, it is characterized in that: the processing procedure number of wafers in described step (4) is not more than the control wafer number in described step (1).
8. remove the method for wafer surface defects in wet etching according to claim 1, it is characterized in that: the processing procedure number of wafers in described step (4) is identical with the control wafer number in described step (1).
9. remove the method for wafer surface defects in wet etching according to claim 1, it is characterized in that: the mass concentration of the phosphoric acid in described step (6) in the second etching tank is 20% ~ 40%.
10. in wet etching according to claim 1, remove the method for wafer surface defects, it is characterized in that: the situation that in described step (6), silicon nitride is the highest to the etching selection ratio of silicon dioxide is: silicon nitride is corroded completely, and silicon dioxide is not corroded completely.
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Cited By (5)

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CN107706192A (en) * 2017-08-22 2018-02-16 长江存储科技有限责任公司 The preparation method and its structure of a kind of three-dimensional storage
CN110047749A (en) * 2019-03-21 2019-07-23 中国电子科技集团公司第五十五研究所 The minimizing technology of silicon nitride in a kind of radio frequency LDMOS flatening process
CN111081787A (en) * 2019-11-20 2020-04-28 广微集成技术(深圳)有限公司 Wafer preparation method
CN113943579A (en) * 2021-10-15 2022-01-18 中国科学院上海微系统与信息技术研究所 Combined etching liquid, etching system and etching method
CN115881529A (en) * 2023-02-06 2023-03-31 合肥新晶集成电路有限公司 Wet etching method, device, system, computer equipment and medium

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Cited By (8)

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CN107706192A (en) * 2017-08-22 2018-02-16 长江存储科技有限责任公司 The preparation method and its structure of a kind of three-dimensional storage
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CN115881529B (en) * 2023-02-06 2023-05-12 合肥新晶集成电路有限公司 Wet etching method, device, system, computer equipment and medium

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