CN111233513A

CN111233513A - Method for modifying bonding surface of zirconia ceramic restoration

Info

Publication number: CN111233513A
Application number: CN202010087605.4A
Authority: CN
Inventors: 刘梅; 章非敏; 严雨欣; 张青红; 胡小坤
Original assignee: Nanjing Medical University
Current assignee: Nanjing University; Nanjing Medical University
Priority date: 2020-02-12
Filing date: 2020-02-12
Publication date: 2020-06-05

Abstract

The invention discloses a method for modifying a bonding surface of a zirconia ceramic restoration, which comprises the following steps: depositing a silicon dioxide film on the bonding surface of the zirconia ceramic restoration by an atomic layer deposition method. According to the modification method, the ALD technology is used for carrying out gas-solid chemical reaction on the bonding surface of the dental zirconia ceramic, a uniform and conformal silicon dioxide film which is stably combined with the ceramic substrate is deposited, and the short-term and long-term bonding strength of the dental zirconia ceramic and resin can be effectively enhanced by combining the use of the silane coupling agent, so that the bonding performance of the zirconia ceramic material is improved; in addition, the ALD technology can also enable the thickness of the thin film on the bonding surface to be accurately controlled to be in a nanometer level; and the deposition reaction temperature is low, and the ceramic substrate performance is not influenced, so that the long-term mechanical performance of the zirconia ceramic restoration body is not influenced, the clinical service life of the zirconia ceramic restoration body is ensured, and the method has important significance for more extensive clinical application of the zirconia ceramic.

Description

Method for modifying bonding surface of zirconia ceramic restoration

Technical Field

The invention relates to a method for modifying a bonding surface of a zirconia ceramic restoration, belonging to the technical field of dental all-ceramic restoration materials.

Background

The tooth defect is a common disease and a frequently encountered disease in the oral cavity repair, and the zirconia ceramic is widely applied to the repair of the tooth defect due to the excellent mechanical property and aesthetic property, good biocompatibility and chemical stability. At present, the zirconia ceramics used in oral clinic are yttria stabilized tetragonal zirconia ceramics (Y-TZP) which are most commonly used and have better mechanical properties, according to in vitro research, the bending strength is 900-1200MPa, the breaking strength is 7-10MPa, and the elastic modulus is about 200GPa, so that the zirconia ceramics can bear complex all-directional occlusal force in the oral cavity.

However, zirconia ceramics with untreated surfaces have low surface energy, poor wettability, high chemical inertness and no chemical bonding with resin adhesives, so that strong and durable bonding is difficult to obtain, and thus the debonding rate of the zirconia ceramic restoration is high.

In order to ensure the life of the restoration and clinical success, it is first necessary to optimize the adhesion properties of the zirconia ceramic. Researchers have proposed that the bonding of zirconia all-ceramic restorations is usually by means of two mechanisms, micro-mechanical locking and chemical bonding. Because zirconia ceramics are chemically inert and cannot react with hydrofluoric acid, the micromechanical locking mechanism usually needs to be realized by sand blasting, which is the conventional treatment at present, namely sand blasting + silicon coating + silane coupling agent. The sintered zirconium dioxide is difficult to form grooves and micro-retention shapes in the pretreatment process due to the ultrahigh surface hardness of the zirconium dioxide, only a small amount of cuts are generated after sand blasting, and the bonding strength obtained only through a micro-mechanical locking retention mechanism cannot meet the clinical requirement. Therefore, there is a need to optimize the use of silicon coatings in combination with silane coupling agents to achieve improved bond strength of zirconia ceramics to resins.

The silicon coating method mainly comprises a sol-gel method, a vapor phase hydrolysis method, an electrostatic self-assembly method, a tribochemical silicon coating method, a plasma spraying method, a silicon tetrachloride vapor method, an atomization deposition method and the like, wherein the silicon dioxide films deposited by the former methods all belong to physical adsorption, the acting force of the combination of the films and the substrate is small, the films are unstable, and the bonding interface is easy to damage; in the latter cases, the surface of zirconia is coated with a silica coating by a specific treatment, and although documents report that the adhesion strength of zirconia can be improved, the adhesion effect needs to be further confirmed because the adhesion strength has not been clinically popularized due to the complicated equipment requirements and procedures.

Disclosure of Invention

The purpose of the invention is as follows: the technical problem to be solved by the invention is to provide a method for modifying the bonding surface of the zirconia ceramic restoration, which improves the short-term and long-term bonding strength of the zirconia ceramic and resin by depositing a nano silicon oxide film on the bonding surface of the zirconia ceramic.

In order to solve the technical problems, the technical scheme adopted by the invention is as follows:

a modification method of a bonding surface of a zirconia ceramic restoration body comprises the following steps: depositing a silicon dioxide film on the bonding surface of the zirconia ceramic restoration by an atomic layer deposition method.

Wherein the deposition thickness of the silicon dioxide film is not less than 9.99 nm.

Wherein, before depositing the silicon dioxide film on the bonding surface of the zirconia ceramic restoration, the bonding surface of the zirconia ceramic needs to be pretreated, and the pretreatment comprises the following steps: sand blasting treatment of the bonding surface of the zirconia ceramic and activation treatment of the bonding surface of the zirconia ceramic.

Wherein the atomic layer deposition method comprises the following steps: the activated zirconia ceramic is put into an atomic layer reaction bin, 3-dimethyl amino silane and ozone are respectively used as gas-solidification chemical reaction precursors, nitrogen is used as cleaning gas, and SiO is circularly deposited at the constant temperature of 200 DEG C₂A film.

The atomic layer deposition method specifically comprises the following steps: placing the activated zirconia ceramic into an atomic layer reaction chamber, introducing 3-dimethyl amino silane precursor pulse for 200ms and nitrogen with the flow of 10sccm for purging for 20s at the constant temperature of 200 ℃, waiting for 5s, and introducing ozone precursor pulse for 1000ms and nitrogen with the flow of 10sccm for purging for 20s at the constant temperature of 200 ℃ after waiting for finishing; waiting for 5s, and after the end of the waiting, introducing 3-dimethyl aminosilane again at a constant temperature of 200 DEG CPurging with nitrogen gas at the flow rate of 10sccm for 20s and 200ms for the precursor pulse, waiting for 5s, and introducing an ozone precursor pulse at the constant temperature of 200 ℃ for 1000ms and purging with nitrogen gas at the flow rate of 10sccm for 20s after the end of the waiting; the above-mentioned processes are repeated, one pulse of 3-dimethyl amino silane precursor for 200ms and one pulse of ozone precursor for 1000ms are used as one cycle, and one cycle is used for depositing SiO once₂Film, SiO finally obtained₂The film is SiO deposited for 200-600 times₂A film.

The pretreated zirconia ceramic is placed in an atomic layer reaction bin, and 1000ms ozone precursor pulse is required to be introduced for 20 times of circulation before the cycle period of depositing the silicon dioxide film is carried out.

The activating agent adopted for activating the bonding surface of the zirconia ceramic is piranha solution, and the piranha solution is prepared from 98 mass percent of concentrated sulfuric acid and 30 mass percent of hydrogen peroxide according to a volume ratio of 7: 3, mixing; the sandblasted zirconia ceramic was immersed in piranha solution and kept in an oil bath at 80 ℃ for 40 min.

Wherein the short-term shearing bonding strength of the zirconia ceramic restoration body with the nano silicon dioxide film deposited on the bonding surface and the resin is 11.76 +/-1.06-16.40 +/-1.60 MPa.

Wherein the long-term shearing bonding strength of the zirconia ceramic restoration body with the nano silicon dioxide film deposited on the bonding surface and the resin is 11.35 +/-0.82-13.53 +/-1.52 MPa.

Has the advantages that: according to the modification method, the silicon dioxide film which is uniform and conformal and is stably combined with the ceramic substrate is deposited on the bonding surface of the dental zirconia ceramic through gas-solidification chemical reaction by an atomic layer deposition method (ALD technology), and a silane coupling agent is used in a combined manner, so that the short-term and long-term bonding strength of the dental zirconia ceramic and resin can be effectively enhanced, and the bonding performance of the zirconia ceramic material is improved; in addition, the ALD technology can also enable the thickness of the thin film on the bonding surface to be accurately controlled to be in a nanometer level; and the deposition reaction temperature is low, and the ceramic substrate performance is not influenced, so that the long-term mechanical performance of the zirconia ceramic restoration body is not influenced, the clinical service life of the zirconia ceramic restoration body is ensured, and the method has important significance for more extensive clinical application of the zirconia ceramic.

Drawings

FIG. 1 is a scanning electron micrograph of a dental zirconia ceramic; wherein, the picture A is a scanning electron microscope picture of the dental zirconia ceramics of the blank control group which is not deposited with the silicon dioxide film; FIG. B shows deposition of 200 cycles of SiO₂Scanning electron micrographs of the thin film dental zirconia ceramic; graph C is the deposition of 400 cycles of SiO₂Scanning electron micrographs of the thin film dental zirconia ceramic; panel D is deposition of 600 cycles of SiO₂Scanning electron micrographs of the thin film dental zirconia ceramic;

FIG. 2 is an elemental energy spectrum of a dental zirconia ceramic; wherein, the graph A is an element energy spectrogram of the dental zirconia ceramic of a blank control group without depositing a silicon dioxide film; FIG. B shows deposition of 200 cycles of SiO₂The element energy spectrum of the dental zirconia ceramic of the film; graph C is the deposition of 400 cycles of SiO₂The element energy spectrum of the dental zirconia ceramic of the film; panel D is deposition of 600 cycles of SiO₂The element energy spectrum of the dental zirconia ceramic of the film;

FIG. 3 is an EDS layered image of a dental zirconia ceramic; wherein, the graph A is an EDS layered image of a blank control group dental zirconia ceramic without a silicon dioxide film deposition; FIG. B shows deposition of 200 cycles of SiO₂EDS layered images of dental zirconia ceramics of thin films; graph C is the deposition of 400 cycles of SiO₂EDS layered images of dental zirconia ceramics of thin films; panel D is deposition of 600 cycles of SiO₂EDS layered images of dental zirconia ceramics of thin films;

FIG. 4 is an atomic force microscope three-dimensional perspective view and a corresponding plan view of a dental zirconia ceramic; wherein, the picture A is an atomic force microscope three-dimensional stereo view and a corresponding plan view of the dental zirconia ceramics of the blank control group without silicon dioxide film deposition; FIG. B shows deposition of 200 cycles of SiO₂An atomic force microscope three-dimensional perspective view and a corresponding plan view of the thin-film dental zirconia ceramic; graph C is the deposition of 400 cycles of SiO₂An atomic force microscope three-dimensional perspective view and a corresponding plan view of the thin-film dental zirconia ceramic; panel D is deposition of 600 cycles of SiO₂Film(s)The atomic force microscope three-dimensional perspective view and the corresponding plan view of the dental zirconia ceramics;

FIG. 5 is a Fourier infrared spectrum of the dental zirconia ceramics obtained from the blank control group and the three experimental groups;

FIG. 6 is a graph showing the average and standard deviation of the short-term and long-term shear strength of the dental zirconia ceramics and the resin obtained from the blank control group and three experimental groups;

FIG. 7 is a graph showing three types of fracture modes of a dental zirconia ceramic bonding interface obtained by a shear test; wherein, figure a₁、b₁、c₁Stereomicroscope images at 1.5 times magnification; FIG. a₂、b₂、c₂Scanning electron microscope images with magnification of 100 times; FIG. a₃、b₃、c₃A scanning electron micrograph at 2000 times magnification;

FIG. 8 is a graph of percent failure mode of dental zirconia ceramic bonded interfaces after 24 hours water bath obtained from a blank control group and three experimental groups;

FIG. 9 is a graph of percentage of failure mode of dental zirconia ceramic bond interfaces after 12000 cycles of cold and heat cycles obtained from a blank control group and three experimental groups.

Detailed Description

The technical solution of the present invention is further explained with reference to the accompanying drawings and specific embodiments.

The invention relates to a method for modifying the bonding surface of a zirconia ceramic restoration, which comprises the following steps:

(1) the method comprises the following steps of pretreating the surface of the zirconia ceramic, wherein the pretreatment comprises the following steps:

and x, sand blasting treatment of the bonding surface of the zirconia ceramic: sintering the zirconia ceramics according to a sintering procedure of a manufacturer, blasting sand for 10s by using 110um alumina particles at a position 10mm away from a bonding surface of the zirconia ceramics under the pressure of 0.3MPa, placing the blasted zirconia ceramics in absolute ethyl alcohol, and ultrasonically cleaning for 20min to remove particles and debris on the surface, and drying the zirconia ceramics by drying in oil-free air;

y. activation treatment of the bonding surface of zirconia ceramics: the zirconia ceramics after sand blasting treatment is dipped in piranha solution (V)_{98% concentrated sulfuric acid}∶V_{30％Hydrogen peroxide solution}7: 3), keeping the mixture in an oil bath at 80 ℃ for 40min, taking out the zirconia ceramic, cleaning the zirconia ceramic with deionized water, and then soaking the zirconia ceramic in a mixed solution (the mixed solution is formed by mixing 28 mass percent of ammonia water, 30 mass percent of hydrogen peroxide and deionized water according to the volume ratio of 1: 5, namely V)_{28% ammonia water}∶V_{30% hydrogen peroxide}∶V_{Deionized water}1: 5), keeping the mixture in an oil bath at 40 ℃ for 30min, taking out the zirconia ceramic from the mixed solution, cleaning the zirconia ceramic by using deionized water, and putting the zirconia ceramic into a drying oven to dry the zirconia ceramic for 1h at 80 ℃ for later use;

(2) depositing a nano silicon dioxide film on the surface of the dental zirconia ceramic by using an ALD (atomic layer deposition) technology, which specifically comprises the following steps:

a. putting the dried zirconia ceramic into an atomic layer reaction bin, and introducing 1000ms ozone precursor pulse for 20 times at the constant temperature of 200 ℃ for circulation so as to activate the surface of the zirconia ceramic;

b. introducing 3-dimethyl amino silane precursor pulse for 200ms and nitrogen with the flow of 10sccm into the activated zirconia ceramic at the constant temperature of 200 ℃ for 20 s;

c. waiting for 5s in the middle;

d. after the end of waiting, introducing ozone precursor pulse for 1000ms and nitrogen with the flow of 10sccm for purging for 20s at the constant temperature of 200 ℃;

e. waiting for 5s in the middle;

f. b-e are repeated and circulated in sequence, one pulse of the 3-dimethyl amino silane precursor for 200ms and one pulse of the ozone precursor for 1000ms are a cycle, and one SiO is deposited in the cycle₂A film; depositing SiO for 200-600 times₂And (3) forming a thin film.

Namely, in the method of the invention, the reaction for depositing the silicon dioxide film is composed of a plurality of cycle periods, each cycle period is divided into two parts, the first part of each cycle period for depositing the silicon dioxide film is a 3-dimethyl amino silane precursor pulse with 200ms and a nitrogen purge with the flow rate of 20s of 10sccm, the second part of each cycle period for depositing the silicon dioxide film is an ozone precursor pulse with the flow rate of 1000ms and a nitrogen purge with the flow rate of 20s of 10sccm, 5s needs to wait between the first part and the second part in each cycle period for depositing the silicon dioxide film, 5s also needs to wait between each cycle, and the cycle period for depositing the silicon dioxide film is carried out for 200 times and 600 times in total.

Deposit 200 cycles of SiO₂The zirconia ceramics of the film are set as an experimental group B, and SiO is deposited for 400 cycles₂The zirconia ceramics of the film are set as an experimental group C, and SiO is deposited for 600 times of circulation₂The zirconia ceramics of the film were set as the experimental group D, while the treatment group in which the silica film was not deposited was set as the blank control group a.

The four groups of zirconia ceramics are ultrasonically washed for 10min by absolute ethyl alcohol, lightly air-dried, installed on a metal pile, gilded, observed by a scanning electron microscope in a vacuum environment, observed in the shape after the zirconia ceramics are subjected to surface treatment under the magnification of 10000, and simultaneously characterized by an energy spectrometer. As a result, as shown in fig. 1, the group a after sandblasting has a rough surface, the zirconia ceramic surface has a large amount of fragments under the impact of the alumina particles, and the surface has irregular gullies and different depths; B. c, D group surface similar to group A, general morphology preservation, SiO₂The layer is deposited according to the rough topography of the substrate, because chemical bonds are formed in the first atomic layer of the substrate, so that the substrate has good reproducibility and adhesion, and the surface characteristics of the substrate can be reproduced very accurately. As the thickness of the deposited film increases, it is seen that the overall roughness decreases even more, deep crevices are filled with the film, and the steep profile becomes relatively flat due to the film coverage. As can be seen in fig. 2 to 3, the B, C, D group was expressed by Si element, but the trace amount thereof was small in the total element distribution diagram, but the Si element content was gradually increased from 0.8% to 1.3% as the number of cycles was increased. And from the group B to the group D, the proportion of the O element increases along with the increase of the Si element, and the two are in a linear correlation relationship.

The atomic force microscope observation in fig. 4 shows that the topography of group a is fluctuant, has large and rough height difference, the height difference in the 3-dimensional perspective view of group B, C, D is increasingly reduced, the gully becomes less deep, the towering topography becomes flatter, and the measured roughness results also confirm the observation of the zirconia ceramic surface topography.

Table 1 shows the surface roughness measured for four groups of zirconia ceramics:

group of	A	B	C	D
					Ra(nm)	63.58	53.63	44.15	42.8

In FIG. 5, infrared spectroscopic analysis of four groups of ceramics revealed that group D was 1077cm^-1An asymmetric stretching vibration peak of Si-O-Si appears, which prompts the formation of Si-O-Si bonds on the surface of the zirconia ceramic and provides a foundation for enhancing the combination of the ceramic and the silane coupling agent. The silane molecule can be hydrolyzed to the silanol, starting from the corresponding-Si-O-CH₃generating-Si-OH, and further reacting with Si-O-Si on the surface of the zirconia ceramic to form a siloxane network. The more Si-O-Si bonds are formed, the stronger the chemical reactivity is, the tighter the siloxane network connection is, and the firmer the bonding of the zirconia ceramic and the silane coupling agent is. On the other hand, the other end of the silane molecule is subjected to radical polymerization with the methacrylate group of the resin binder, and the zirconia ceramic is bonded to the resin by the formation of these chemical bondsAnd (3) preparing. As the number of cycles decreased, the peak of the stretching vibration peak intensity of Si-O-Si decreased, which was weaker in 200 cycles (group B) and 400 cycles (group C); while this peak was not present in group a.

The thickness of the silicon dioxide film obtained after the ALD technology deposits on the surface of the zirconia ceramic for 200-600 cycles is respectively 9.99nm, 18.03nm and 26.58nm, which proves that the silicon dioxide film deposited by the ALD technology is accurate to the nanometer level. In addition, the thickness per cycle of the group B was 0.04995nm/cycle, the thickness per cycle of the group C was 0.04508nm/cycle, the thickness per cycle of the group D was 0.04430nm/cycle, and the thickness of the silicon dioxide film deposited per cycle of each group was similar, indicating the uniformity of the film deposited by ALD technique.

Table 2 shows the thickness of the silicon dioxide film obtained after the ALD technique deposits on the surface of the zirconia ceramic for 200-600 cycles:

group of	B	C	D
				Film thickness (nm)	9.99	18.03	26.58

The method disclosed by the invention is applied to enhancing the short-term and long-term bonding strength between dental zirconia ceramics and resin as follows:

four groups (A group, B group, C group and D group) are respectively made into 64 photocuring composite resin cylinders with the diameter of 6mm and the height of 2mm for later use.

And (3) coating a silane coupling agent on 64 zirconium oxide ceramic chips prepared in each group, volatilizing freely for 30s, and drying by drying in oilless air. Then coating a porcelain adhesive, freely volatilizing for 30s, and drying by air without oil. Then coating a thin layer of light-cured composite resin cement on each ceramic sheet, placing a composite resin column on the resin cement in a pressing mode, continuously pressing for 10s, removing redundant resin cement along the edge, and performing light curing for 20s in the front direction, the rear direction, the left direction, the right direction and the top direction of each resin column.

After each group of prepared test pieces (n is 64) is put into a water bath for 24 hours, one half (n is 32) of the test pieces in each group are randomly selected for 12000 times of cold and hot circulation (5 ℃ -55 ℃), and the test pieces are embedded by self-setting plastics. Placing all the test pieces in a universal testing machine, adjusting a loading head to enable the direction of a shearing blade to be parallel to the bonding surface of the resin ceramic, setting the loading speed to be 1mm/min, recording the maximum load F required by the falling of each resin cylinder on the four groups of zirconia ceramics, and calculating the formula that the bonding strength (MPa) is the maximum load (N)/the area (mm) according to the anti-shearing bonding strength²) "calculate shear adhesion strength value.

And (5) carrying out statistical analysis on the bonding strength data of each group by using a one-factor variance analysis and a Tukey's HSD pairwise comparison method according to the test result of each group of shearing experiments (the mean value and the standard deviation of the shearing bonding strength values are shown in figure 6). After 24 water bath, the difference between the groups except B and C is statistically significant (P is more than 0.05), wherein the bonding strength of the group D is the highest (16.49 +/-1.60 MPa) and the bonding strength of the group A is the lowest (7.05 +/-0.91 MPa). After 12000 times of cold and hot cycles, the bonding strength of each group is reduced to different degrees, and the reduction range of the group C is the minimum (0.41 MPa). The adhesive strength of group D was still the highest (13.53. + -. 1.52MPa), and the adhesive strength of group A was still the lowest (3.46. + -. 1.85 MPa). It is demonstrated that the application of the ALD technique greatly improves the bonding strength of the dental zirconia ceramic to the resin, whether it is cycled less than 200 times or more than 600 times. This is because of the SiO deposited by ALD₂The film is connected with the zirconia ceramic substrate through chemical bond energy generated by gas-solidification chemical reaction, promotes the combination of the film and the ceramic substrate and is favorable for resisting coldHydrolytic degradation and thermal stress effects in thermal cycling. In addition, the ultra-thinness of films deposited by ALD can be further reduced due to SiO₂The adhesive interface is broken due to instability of the film layer. Wherein the short-term and long-term bonding strength improved by 600 cycles is the highest, and the adhesive can be suitable for long-term use in the moist and warm environment of the oral cavity.

Table 3 shows the mean, standard deviation and 95% confidence intervals of the shear adhesion strength values obtained in the four zirconia ceramic tests:

placing four groups of zirconia ceramic bonding surfaces subjected to a shearing experiment in a stereoscopic microscope, observing the morphology of the bonding surfaces subjected to loading fracture under the magnification of 1.5 times, recording the bonding fracture mode, further observing the fracture surfaces under the magnification of 100 times and 2000 times by using a scanning electron microscope, and recording the fracture modes as three types, as shown in fig. 7: (a) interfacial/adhesive failure: the damage is generated in a zirconium oxide/resin interface or an adhesive, a ceramic bonding surface is exposed, and the residual amount of the resin composite material is less than 33%; (b) cohesive failure: more than 66% of the resin composite material is remained on the surface of the zirconia; (c) and (3) mixing and breaking: both failures occur simultaneously, partially exposing the ceramic bonding surface, leaving more than 33% but less than 66% of the resin composite remaining on the ceramic surface. Four sets of failure mode observations are shown in fig. 8 and 9: after 24 hours in the water bath, the failure mode of group a was 85.7% cohesive failure, while the cohesive failure ratios of B, C, D were all less than 50%, predominantly the mixed failure mode, and the cohesive failure mode was present in all B, C, D experimental groups. After 12000 cycles of cooling and heating, group a showed only adhesive failure, and the adhesive failure ratio of group B, C, D decreased gradually, still dominated by mixing failure. And group D showed only two modes of mixed and cohesive failure, with no adhesive failure. Clinically, mixed and cohesive failure is preferred over adhesive failure, as adhesive failure is often associated with lower bond strength, a result that further evidences the use of ALD techniques to effectively improve the short and long term bond strength of dental zirconia ceramics to resins.

Claims

1. A method for modifying the bonding surface of a zirconia ceramic restoration is characterized by comprising the following steps: the modification method comprises the following steps: depositing a silicon dioxide film on the bonding surface of the zirconia ceramic restoration by an atomic layer deposition method.

2. The method for modifying the adhesion surface of a zirconia ceramic restoration according to claim 1, wherein: the deposition thickness of the silicon dioxide film is not less than 9.99 nm.

3. The method for modifying the adhesion surface of a zirconia ceramic restoration according to claim 2, wherein: before depositing a silicon dioxide film on the bonding surface of the zirconia ceramic restoration, the bonding surface of the zirconia ceramic needs to be pretreated, and the pretreatment comprises the following steps: sand blasting treatment of the bonding surface of the zirconia ceramic and activation treatment of the bonding surface of the zirconia ceramic.

4. The method for modifying an adhesion surface of a zirconia ceramic restoration according to claim 3, wherein: the atomic layer deposition method comprises the following steps: the activated zirconia ceramic is put into an atomic layer reaction bin, 3-dimethyl amino silane and ozone are respectively used as gas-solidification chemical reaction precursors, nitrogen is used as cleaning gas, and SiO is circularly deposited at the constant temperature of 200 DEG C₂A film.

5. The method for modifying the adhesion surface of a zirconia ceramic restoration according to claim 4, wherein the atomic layer deposition method is specifically: placing the activated zirconia ceramic into an atomic layer reaction chamber, introducing 3-dimethyl amino silane precursor pulse for 200ms and nitrogen with the flow of 10sccm for purging for 20s at the constant temperature of 200 ℃, waiting for 5s, and introducing ozone precursor pulse for 1000ms and nitrogen with the flow of 10sccm for purging for 20s at the constant temperature of 200 ℃ after waiting for finishing; waiting for 5s, after the waiting, introducing 3-dimethyl amino silane precursor pulse for 200ms again at the constant temperature of 200 DEG CPurging with nitrogen at the flow rate of 10sccm for 20s, waiting for 5s, and after the end of the waiting, introducing ozone precursor pulse for 1000ms and purging with nitrogen at the flow rate of 10sccm for 20s at the constant temperature of 200 ℃; the above-mentioned processes are repeated, one pulse of 3-dimethyl amino silane precursor for 200ms and one pulse of ozone precursor for 1000ms are used as one cycle, and one cycle is used for depositing SiO once₂Film, SiO finally obtained₂The film is SiO deposited for 200-600 times₂A film.

6. The method for modifying an adhesion surface of a zirconia ceramic restoration according to claim 5, wherein: and (3) putting the pretreated zirconia ceramic into an atomic layer reaction bin, and introducing 1000ms ozone precursor pulse for 20 times of circulation before the cycle period of depositing the silicon dioxide film.

7. The method for modifying an adhesion surface of a zirconia ceramic restoration according to claim 3, wherein: activating agent adopted in the activation treatment of the bonding surface of the zirconia ceramics is piranha solution, and the piranha solution is formed by mixing concentrated sulfuric acid with mass fraction of 98% and hydrogen peroxide with mass fraction of 30% according to the volume ratio of 7: 3; the sandblasted zirconia ceramic was immersed in piranha solution and kept in an oil bath at 80 ℃ for 40 min.

8. The method for modifying the adhesion surface of a zirconia ceramic restoration according to claim 2, wherein: the short-term shearing bonding strength of the zirconia ceramic restoration body with the nano silicon dioxide film deposited on the bonding surface and the resin is 11.76 +/-1.06-16.40 +/-1.60 MPa.

9. The method for modifying the adhesion surface of a zirconia ceramic restoration according to claim 2, wherein: the long-term shearing bonding strength of the zirconia ceramic restoration body with the nano silicon dioxide film deposited on the bonding surface and the resin is 11.35 +/-0.82-13.53 +/-1.52 MPa.