Disclosure of Invention
The embodiment of the disclosure provides a preparation method of a tantalum nitride film and a semiconductor device, which can effectively control the corrosion rate of the tantalum nitride film and improve the corrosion uniformity of the tantalum nitride film. The technical scheme is as follows:
In a first aspect, an embodiment of the present disclosure provides a method for preparing a tantalum nitride film, the method comprising:
providing a primary etching solution for dissolving an oxide;
Immersing the tantalum nitride sample in the primary etching solution;
providing a secondary corrosion solution which is a mixed solution of ammonia water, hydrogen peroxide and pure water;
and immersing the tantalum nitride sample in the secondary corrosion solution, and corroding to obtain the tantalum nitride film.
In one implementation of the present disclosure, immersing the tantalum nitride sample in the primary etching solution comprises:
And immersing the tantalum nitride sample in the primary corrosion solution for 3-5 minutes.
In one implementation of the present disclosure, immersing the tantalum nitride sample in the primary etching solution further comprises:
During the immersing of the tantalum nitride sample, the primary etching solution is stirred.
In another implementation of the present disclosure, after immersing the tantalum nitride sample in the primary etching solution, comprising:
Taking the tantalum nitride sample out of the primary corrosion solution;
The tantalum nitride sample was rinsed with deionized water.
In yet another implementation of the present disclosure, providing a secondary etching solution includes:
and mixing the ammonia water, the hydrogen peroxide and the pure water according to the proportion of 1:4:20 to obtain the secondary corrosion solution.
In yet another implementation of the present disclosure, prior to immersing the tantalum nitride sample in the secondary etching solution, comprising:
and adjusting the temperature of the secondary corrosion solution to 60-70 ℃.
In yet another implementation of the present disclosure, immersing the tantalum nitride sample in the secondary corrosion solution comprises:
And immersing the tantalum nitride sample in the secondary corrosion solution for 10-15 minutes.
In yet another implementation of the present disclosure, after immersing the tantalum nitride sample in the secondary etching solution, comprises:
Taking the tantalum nitride sample out of the secondary corrosion solution;
The tantalum nitride sample was rinsed with deionized water.
In yet another implementation of the present disclosure, after rinsing the tantalum nitride sample with deionized water, comprising:
And drying the tantalum nitride sample to obtain a tantalum nitride film.
In a second aspect, embodiments of the present disclosure provide a semiconductor device including a tantalum nitride film obtained by the manufacturing method of the first aspect.
The technical scheme provided by the embodiment of the disclosure has the beneficial effects that:
By the preparation method provided by the embodiment of the disclosure, the tantalum nitride material can be corroded to obtain the required tantalum nitride film. In the preparation process, a primary etching solution is firstly provided, and a tantalum nitride sample is soaked in the primary etching solution. The primary etching solution can dissolve the oxide, so that the tantalum nitride sample is soaked in the primary etching solution, and the oxide on the surface of the tantalum nitride sample can be removed through the primary etching solution, thereby providing a foundation for the subsequent etching process. A secondary etching solution is then provided and the tantalum nitride sample is immersed in the secondary etching solution. The secondary corrosion solution is a mixed solution of ammonia water, hydrogen peroxide and pure water, so that the tantalum nitride sample immersed in the secondary corrosion solution can be corroded. And the characteristics of ammonia water and hydrogen peroxide are benefited, so that the secondary corrosion solution can realize uniform corrosion of the tantalum oxide sample.
In addition, as the oxide on the surface of the tantalum nitride sample is removed through the primary etching solution in advance, the etching rate of the tantalum nitride sample is not influenced by the oxide in the process of etching the tantalum nitride sample through the secondary etching solution, and the accurate control of the etching rate of the tantalum nitride sample is facilitated.
That is, by the preparation method provided by the embodiment of the disclosure, the corrosion rate of the tantalum nitride film can be effectively controlled, and the corrosion uniformity of the tantalum nitride film can be improved, so that the process requirement can be met.
Detailed Description
For the purposes of clarity, technical solutions and advantages of the present disclosure, the following further details the embodiments of the present disclosure with reference to the accompanying drawings.
An embodiment of the present disclosure provides a method for preparing a tantalum nitride film, fig. 1 is a flowchart of the method, and referring to fig. 1, in this embodiment, the method includes:
Step 101, providing a primary etching solution.
Wherein the primary etching solution is used for dissolving the oxide.
Step 102, immersing the tantalum nitride sample in a primary etching solution.
Step 103, providing a secondary etching solution.
Wherein the secondary corrosion solution is a mixed solution of ammonia water, hydrogen peroxide and pure water.
And 104, soaking the tantalum nitride sample in a secondary corrosion solution, and corroding to obtain the tantalum nitride film.
By the preparation method provided by the embodiment of the disclosure, the tantalum nitride material can be corroded to obtain the required tantalum nitride film. In the preparation process, a primary etching solution is firstly provided, and a tantalum nitride sample is soaked in the primary etching solution. The primary etching solution can dissolve the oxide, so that the tantalum nitride sample is soaked in the primary etching solution, and the oxide on the surface of the tantalum nitride sample can be removed through the primary etching solution, thereby providing a foundation for the subsequent etching process. A secondary etching solution is then provided and the tantalum nitride sample is immersed in the secondary etching solution. The secondary corrosion solution is a mixed solution of ammonia water, hydrogen peroxide and pure water, so that the tantalum nitride sample immersed in the secondary corrosion solution can be corroded. And the characteristics of ammonia water and hydrogen peroxide are benefited, so that the secondary corrosion solution can realize uniform corrosion of the tantalum oxide sample. In addition, as the oxide on the surface of the tantalum nitride sample is removed through the primary etching solution in advance, the etching rate of the tantalum nitride sample is not influenced by the oxide in the process of etching the tantalum nitride sample through the secondary etching solution, and the accurate control of the etching rate of the tantalum nitride sample is facilitated.
That is, by the preparation method provided by the embodiment of the disclosure, the corrosion rate of the tantalum nitride film can be effectively controlled, and the corrosion uniformity of the tantalum nitride film can be improved, so that the process requirement can be met.
Fig. 2 is a flowchart of another preparation method of a tantalum nitride film according to an embodiment of the disclosure, referring to fig. 2, in this embodiment, the preparation method includes:
step 201, providing a primary etching solution.
Wherein the primary etching solution is used for dissolving the oxide.
Illustratively, the primary etching solution is a strongly acidic solution, such as a hydrochloric acid solution or the like. In this way, the oxide can be effectively dissolved by the primary etching solution.
It should be noted that the oxide on the surface of the tantalum oxide sample is typically tantalum pentoxide, and the hydrochloric acid solution can generate chemical reaction with the tantalum pentoxide, so as to dissolve the tantalum pentoxide. The chemical formula is as follows:
Ta2O5+10HCl=2TaCl5+5H2O。
step 202, immersing a tantalum nitride sample in a primary etching solution.
In the implementation mode, the tantalum nitride sample is placed in a container where the primary etching solution is located, so that the tantalum nitride sample is ensured to be completely soaked in the primary etching solution. Since the primary etching solution can dissolve oxides, oxides possibly present on the surface of the tantalum nitride sample can be removed by the primary etching solution. In addition, the primary corrosion solution does not have excessive influence on the tantalum nitride sample.
In addition, as the oxide on the surface of the tantalum nitride sample is removed through the primary etching solution, the etching rate of the tantalum nitride sample is not affected by the oxide in the subsequent etching process of the tantalum nitride sample through the secondary etching solution, and the accurate control of the etching rate of the tantalum nitride sample is facilitated.
Illustratively, the tantalum nitride sample is immersed in the primary etching solution for 3-5 minutes.
In the implementation manner, the soaking time of the tantalum nitride sample is controlled to be 3-5 minutes, so that on one hand, the primary corrosion solution can be ensured to fully dissolve oxides on the surface of the tantalum nitride sample, and on the other hand, the primary corrosion solution can be prevented from causing excessive influence on the tantalum oxide sample.
In this example, a tantalum nitride sample was immersed in a primary etching solution for 3 minutes. Of course, in other embodiments, other durations within the above-described range of durations are possible, such as 5 minutes, etc., which the present disclosure is not limited to.
In this example, the etching solution was stirred once during the immersion of the tantalum nitride sample.
In this way, the sufficient reaction between the primary etching solution and the oxide can be ensured, so that the primary etching solution can uniformly dissolve the oxide on the surface of the tantalum nitride sample.
It should be noted that the stirring time period can also be selected according to practical situations, and this disclosure is not limited thereto.
And 203, taking out the tantalum nitride sample from the primary etching solution, and flushing the tantalum nitride sample with deionized water.
In the implementation manner, the tantalum nitride sample is rinsed by deionized water so as to clean the primary etching solution remained on the surface of the tantalum nitride sample.
Step 204, providing a secondary etching solution.
Wherein the secondary corrosion solution is a mixed solution of ammonia water, hydrogen peroxide and pure water.
In the implementation mode, the characteristics of ammonia water and hydrogen peroxide are utilized, so that the tantalum nitride sample can be effectively corroded.
The secondary etching solution will now be described for the etching principle of tantalum nitride.
Ammonia is a weak base. In aqueous solution, it partially ionizes to give ammonium ions and hydroxide ions. During etching of tantalum nitride, hydroxyl ions can react with the tantalum nitride surface. For example, it may form some hydroxide complexes of tantalum with tantalum element in tantalum nitride, thereby breaking the surface structure of tantalum nitride.
Hydrogen peroxide is a strong oxidizer. In solution, it can decompose to generate reactive oxygen species with strong oxidizing properties, such as hydroxyl radicals. The hydroxyl radical has high reactivity and can attack chemical bonds on the surface of tantalum nitride. The method can react with nitrogen-tantalum bonds in the tantalum nitride to separate nitrogen elements in the form of nitrogen-containing compounds, and the tantalum elements are oxidized, so that the corrosion process of the tantalum nitride is accelerated.
In this example, ammonia, hydrogen peroxide and pure water were mixed in a ratio of 1:4:20 to obtain a secondary etching solution.
In the process of preparing the secondary corrosion solution, firstly, a proper amount of ammonia water is measured and poured into a reaction container, then, hydrogen peroxide with corresponding volume is added, and finally, water with specified volume is added, and the stirring is uniform, so that the solution is fully mixed.
In the implementation mode, the ammonia water, the hydrogen peroxide and the pure water are mixed according to the proportion of 1:4:20, and the following components are mixed
The beneficial effects are that:
(1) The hydrogen peroxide has strong oxidizing property and can perform oxidation reaction with the tantalum nitride, so that chemical bonds on the surface of the tantalum nitride are broken, and corrosion is realized. The ammonia water is weakly alkaline, can promote the decomposition of hydrogen peroxide, generate more active substances such as hydroxyl free radicals with strong oxidability, accelerate the corrosion process, and the two are synergistic, so that the tantalum nitride can be effectively corroded, the surface of the tantalum nitride can form a specific microstructure or reach the required roughness, and different application requirements are met.
(2) The corrosion uniformity is high, and under the proportion of the ammonia water, the hydrogen peroxide and the pure water, the components of the solution are distributed relatively uniformly, so that the corrosion reaction can be uniformly carried out on the surface of the tantalum nitride, the excessive or insufficient local corrosion is avoided, the uniformity of the quality and the performance of the surface of the tantalum nitride is ensured, and the follow-up accurate processing and use of the tantalum nitride material are facilitated.
(3) The corrosion rate is easy to control, and the corrosion rate can be controlled more accurately in a certain range by adjusting the conditions such as reaction temperature, time and the like. If the temperature is increased, the molecular movement is accelerated, the reaction rate is increased, and if the temperature is reduced, the reaction rate is slowed down, and the reaction rate is conveniently and flexibly adjusted according to specific requirements, so that the ideal corrosion effect is obtained.
(4) The operation is relatively safe, the corrosiveness of the secondary corrosion solution in the proportion is relatively mild, compared with some corrosives with strong corrosives, the harm to operators and equipment is small, the operation can be performed under the conventional experimental condition, special protective equipment and harsh operation environments are not needed, and the experimental cost and the operation difficulty are reduced.
(5) The secondary corrosion solution with the proportion is relatively environment-friendly, the components of the secondary corrosion solution are easy to decompose or treat in the natural environment, harmful substances which are difficult to degrade are not generated, the pollution to the environment is small, the development concept of green chemistry is met, and the negative influence on the environment is reduced.
And 205, adjusting the temperature of the secondary corrosion solution to 60-70 ℃.
The secondary corrosion solution is added into a heating container, and the secondary corrosion solution is heated through the heating container, so that the temperature of the secondary corrosion solution reaches 60-70 ℃.
In the temperature range, the secondary corrosion solution can sufficiently corrode the tantalum nitride sample so as to ensure higher corrosion efficiency.
The temperature is increased to 60-70 ℃, so that the chemical reaction rate can be accelerated. According to the Arrhenii Wu Sigong, the reaction rate constant k increases as the temperature increases. For the reaction of ammonia water and tantalum nitride and the reaction of hydrogen peroxide and tantalum nitride, after the temperature is increased, the speed of ionization of the ammonia water to generate hydroxide ions is increased, and the speed of decomposition of the hydrogen peroxide to generate hydroxyl free radicals is also increased. Moreover, the increased temperature accelerates the diffusion rate of these active species (hydroxyl ions, hydroxyl radicals, etc.) in the solution, which can more frequently contact and react with the surface of the tantalum nitride sample, thereby enhancing the corrosion effect on the tantalum nitride sample.
In this embodiment, the temperature of the secondary etching solution is adjusted to 65 degrees celsius. Of course, in other embodiments, the temperature of the secondary etching solution can also be adjusted to other temperatures within the above temperature range, which is not limited by the present disclosure.
Illustratively, the heating vessel is a high temperature resistant and corrosion resistant reaction vessel, such as a polytetrafluoroethylene-lined stainless steel reaction kettle, to withstand temperatures of 60-70 ℃ and corrosiveness of the solution.
Step 206, immersing the tantalum nitride sample in the secondary etching solution.
In the implementation mode, the tantalum nitride sample is placed in a container where the secondary corrosion solution is located, so that the tantalum nitride sample is ensured to be completely soaked in the secondary corrosion solution. The secondary corrosion solution is a mixed solution of ammonia water, hydrogen peroxide and pure water, so that the tantalum nitride sample can be uniformly and efficiently corroded.
Illustratively, the tantalum nitride sample is immersed in the secondary etching solution for 10-15 minutes.
In the implementation mode, the soaking time of the tantalum nitride sample is controlled to be 10-15 minutes, so that on one hand, the tantalum nitride sample can be fully corroded by the secondary corrosion solution according to expectations, and on the other hand, excessive corrosion can be avoided.
In this example, a tantalum nitride sample was immersed in the secondary etching solution for 12 minutes. Of course, in other embodiments, other durations within the above-described range of durations are possible, such as 14 minutes, etc., which the present disclosure is not limited to.
It is worth noting that during the process of etching the tantalum nitride sample by the secondary etching solution, the state of the secondary etching solution and the condition of the tantalum nitride sample are continuously detected, and the etching process is ensured to be carried out according to an expected plan.
Step 207, taking the tantalum nitride sample out of the secondary etching solution, and flushing the tantalum nitride sample with deionized water.
In the implementation manner, the tantalum nitride sample is rinsed by deionized water so as to clean the secondary etching solution remained on the surface of the tantalum nitride sample.
And step 208, drying the tantalum nitride sample to obtain the tantalum nitride film.
In the implementation manner, the deionized water remained on the surface of the tantalum nitride sample is dried to obtain the final tantalum nitride film.
The preparation method provided by the embodiment of the disclosure can improve the corrosion uniformity and is beneficial to controlling the corrosion rate. The following description will be given respectively:
with respect to improving corrosion uniformity:
(1) The uniformity of the solution mixing is enhanced.
The temperature is increased to 60-70 ℃ so as to accelerate the convection and diffusion processes of the secondary corrosion solution. The thermal movement of the molecules becomes more intense when the secondary etching solution is heated. This makes the ammonia water and hydrogen peroxide in the secondary corrosion solution more evenly distributed in the whole reaction system. For example, under the condition of no heating, the solution may cause non-uniformity of corrosion due to local concentration difference, but at 60-70 ℃, the concentration difference is reduced due to rapid diffusion, so that the etchant is distributed more uniformly on the surface of the tantalum nitride, and further the uniformity of corrosion is improved.
(2) Uniform activation of reactive sites.
There are many potential reactive sites on the tantalum nitride surface. And at the temperature of 60-70 ℃, the activity of ammonia water and hydrogen peroxide is enhanced. On one hand, hydroxide ions ionized from ammonia water can better interact with metal atoms on the surface of tantalum nitride, and active oxygen species generated by hydrogen peroxide can also attack chemical bonds on the surface of tantalum nitride more uniformly. The temperature rise enables the reactions to start at all positions on the tantalum nitride surface more synchronously, and the situation that local reactions are too fast or too slow can not occur, so that the uniformity of corrosion can be improved.
For aspects advantageous in controlling the corrosion rate:
(1) Application of Arrhenius formula.
From the Arrhenii Wu Sigong equation, temperature is an important factor affecting the reaction rate constant. In this system, the reaction rate constant will stabilize at a relatively predictable value when the temperature is stabilized at 60-70 degrees celsius. This is because the increase in temperature accelerates the reaction rate based on the quantitative relationship of this formula. The corrosion rate can be estimated and controlled approximately by these parameters as long as the conditions of temperature, ammonia concentration, hydrogen peroxide concentration, etc. are kept relatively stable. For example, if the corrosion rate is found to be too fast, the temperature can be appropriately reduced or the concentration of ammonia water and hydrogen peroxide can be reduced to adjust.
(2) The observability of the reaction process is enhanced.
At 60-70 ℃, the reaction rate is moderate, the corrosion process is not too slow and difficult to observe due to the too low temperature, and the reaction is not completed instantly and cannot be controlled due to the too high temperature. Such temperature conditions facilitate laboratory personnel to monitor the corrosion process in real time. The corrosion process can be tracked by observing the color change of the solution, the gas generation condition or measuring the mass loss of tantalum nitride, and the reaction condition can be timely adjusted according to the observation result, so that the corrosion rate can be effectively controlled.
Unless defined otherwise, technical or scientific terms used herein should be given the ordinary meaning as understood by one of ordinary skill in the art to which this disclosure belongs. The terms "first," "second," "third," and the like in the description and in the claims, do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. Likewise, the terms "a" or "an" and the like do not denote a limitation of quantity, but rather denote the presence of at least one. The word "comprising" or "comprises", and the like, is intended to mean that elements or items that are present in front of "comprising" or "comprising" are included in the word "comprising" or "comprising", and equivalents thereof, without excluding other elements or items. The terms "connected" or "connected," and the like, are not limited to physical or mechanical connections, but may include electrical connections, whether direct or indirect. "upper", "lower", "left", "right", etc. are used merely to indicate relative positional relationships, and when the absolute position of the object to be described is changed, the relative positional relationships may be changed accordingly.
The foregoing description of the preferred embodiments of the present disclosure is provided for the purpose of illustration only, and is not intended to limit the disclosure to the particular embodiments disclosed, but on the contrary, the intention is to cover all modifications, equivalents, alternatives, and alternatives falling within the spirit and principles of the disclosure.