CN113314342B - Method for improving energy storage density of dielectric film capacitor and dielectric film capacitor - Google Patents
Method for improving energy storage density of dielectric film capacitor and dielectric film capacitor Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/33—Thin- or thick-film capacitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/10—Metal-oxide dielectrics
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- Microelectronics & Electronic Packaging (AREA)
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- Ceramic Capacitors (AREA)
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Abstract
The invention provides a method for improving the energy storage density of a dielectric film capacitor, which comprises the following steps: s1: preparing a bottom electrode; s2: deposition of PbZrO on bottom electrode 3 A film; s3: to PbZrO 3 Implanting helium ions; s4: and preparing a top electrode. The method for improving the energy storage density of the dielectric film capacitor improves the antiferroelectric material PbZrO 3 The saturation polarization value and the breakdown electric field of the capacitor per se, and the dielectric film capacitor with high energy storage density is obtained.
Description
Technical Field
The invention belongs to the technical field of thin film materials, and particularly relates to a method for improving the energy storage density of a dielectric thin film capacitor and the dielectric thin film capacitor.
Background
The capacitor is a basic energy storage device, and the development trend of miniaturization, integration and portability of products in the electronic industry puts higher requirements on the performance of the capacitor. Due to antiferroelectric material lead zirconate PbZrO 3 (PZO for short) can generate reversible antiferroelectric-ferroelectric phase transition under an electric field, and lead zirconate can be made into a dielectric container with high power density and ultra-fast charge and discharge rate. The current research on lead zirconate as a dielectric container is mainly focused on the doping of the components and the design of nanostructures. The doping of the component is mainly to PbZrO 3 The elements such as lanthanum (La), titanium (Ti), tin (Sn) and the like are added, so that the energy loss in the phase change process can be reduced, the saturation polarization strength is improved, and the energy storage density and efficiency are improved. The design of the nano structure is various, and the multilayer structure, the core-shell structure, the self-assembled nano column, the doped nano particles and the like improve the breakdown electric field of the PZO, reduce leakage current and enhance the energy storage performance.
The PZO-based materials currently used as dielectric containers are mainly classified into two types, ceramic and thin film. The ceramic has high density, poor flexibility and high sintering temperature, so that the application of the ceramic in integrated circuits is limited; in addition, the ceramic is easy to be sinteredVarious defects such as voids and the like are generated, mechanical properties thereof are degraded, and breakdown is easily caused. The film has small volume and strong pressure resistance, meets the requirements of miniaturization and integration of electronic products, but the pure PZO film has low energy storage density (14J/cm) 3 ) The current commercialization requirement is not sufficiently supported, and a large amount of energy is consumed to induce the antiferroelectric-ferroelectric phase transition of PZO through an external electric field, so that deformation is caused, and the energy storage efficiency of the thin film is low and the device is unstable.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a method for improving the energy storage density of a dielectric film capacitor, which improves the antiferroelectric material PbZrO 3 The saturation polarization value and the breakdown electric field of the capacitor per se, and the dielectric film capacitor with high energy storage density is obtained.
The invention is realized by the following technical scheme:
a method for increasing the energy storage density of a dielectric film capacitor comprises the following steps: s1; preparing a bottom electrode; s2: deposition of PbZrO on bottom electrode 3 A film; s3: to PbZrO 3 Implanting helium ions; s4: and preparing a top electrode.
The method for improving the energy storage density of the dielectric film capacitor provided by the invention is to antiferroelectric material PbZrO 3 Implanting helium ions into the PbZrO 3 Lead PbZrO to be in lattice 3 Crystal lattice distortion and destruction of PbZrO 3 The long-range order of dipoles in the crystal, under the action of an electric field between a top electrode and a bottom electrode, PbZrO 3 The orientation of the dipoles in the crystal is consistent in a short range, so that the crystal has relaxation ferroelectric property, helium ions do not replace atoms of the original lattice position, and PbZrO is greatly improved 3 The saturation polarization value and the breakdown electric field of the capacitor per se, and the dielectric film capacitor with high energy storage density is obtained.
Further, PbZrO 3 The thickness of the film is 50-100nm, and if the film is too thin, the leakage current is too large, which is easy to cause heating damage, and if the film is too thick, the miniaturization of the device is not facilitated.
Further, the dose range of the helium ions implanted in S3 is 5 × 10 14 ～5×10 15 ions/cm 2 . The implantation dosage of helium ions should be moderate, and if the dosage is too low, PbZrO should be added 3 The crystal distortion is not enough to break the long-range order of the dipole, and the PbZrO is damaged when the dosage is too high 3 The integrity of the crystal lattice causes amorphization.
Further, the implantation energy of helium ions in S3 is 11-22 keV. The implantation energy should be moderate, and if the implantation energy is too low, helium ions may not be implanted into the crystal lattice and stay in the PbZrO 3 The crystal grain surface is distributed unevenly; when the implantation energy is too high, helium ions penetrate PbZrO 3 The substrate entering the bottom electrode and the lower layer of the bottom electrode cannot stay in the PbZrO 3 Inside.
Further, to PbZrO 3 When injecting helium ions, the incident direction of the helium ions and PbZrO 3 A deflection angle is formed in the main crystal axis direction of the crystal so as to increase the probability of collision between helium ions and crystal lattice atoms, the movement direction of the helium ions after collision is more random, and the helium ions are more uniformly distributed in the crystal lattice.
Furthermore, the deflection angle is 7-10 degrees, if helium ions are injected along the main crystal axis direction of the crystal, the deflection of the helium ions after the helium ions collide with the crystal lattice is small, and the helium ions can enter the interior of the crystal lattice and even penetrate through PbZrO 3 Film, i.e. producing channeling, according to PbZrO 3 The internal crystal structure sets the deflection angle to avoid channeling.
Further, the bottom electrode is a perovskite-type conductive oxide. The bottom electrode is selected to ensure PbZrO 3 Antiferroelectricity can be epitaxially grown and maintained on the bottom electrode.
Further, in S1, a bottom electrode is deposited on the substrate, the substrate being a perovskite-type material, the bottom electrode being grown on the substrate by selecting a suitable substrate.
Further, in S2, PbZrO is deposited on the bottom electrode using pulsed laser deposition 3 Film to ensure deposition of the resulting PbZrO 3 Has a single crystal structure and less crystal defects, and PbZrO 3 The film has good performance and is beneficial to uniformly injecting helium ions into PbZrO 3 Inside the crystal, if PbZrO 3 The film is a polycrystalline structure, so that the helium ion capacity is increased when the helium ions are implantedEasy to inject into the interface between the grains.
The invention also provides a dielectric film capacitor comprising a top electrode, a bottom electrode and PbZrO 3 Film of PbZrO 3 A thin film is positioned between the top electrode and the bottom electrode; the PbZrO 3 The film comprises PbZrO 3 Crystal and helium ion, the helium ion is located in PbZrO 3 Inside the crystal. The dielectric film capacitor of the invention improves PbZrO 3 The saturated polarization value and the breakdown electric field of the capacitor per se obtain the dielectric film capacitor with high energy storage density, the preparation process is stable and controllable, and the trend of miniaturization and integration of electronic devices is met.
For a better understanding and practice, the invention is described in detail below with reference to the accompanying drawings.
Drawings
FIG. 1 is a schematic process flow diagram of a method for increasing the energy storage density of a dielectric thin film capacitor.
Fig. 2 is an XRD pattern of the dielectric thin film capacitor.
FIG. 3 is a ferroelectric hysteresis loop of a dielectric thin film capacitor.
Fig. 4 is a graph of the energy storage density of a dielectric thin film capacitor as a function of the electric field.
Fig. 5 is a weil distribution diagram of breakdown strength of the dielectric thin film capacitor.
Detailed Description
A method for increasing the energy storage density of a dielectric film capacitor, as shown in fig. 1, comprises the following steps:
s1; preparing a bottom electrode;
s2: deposition of PbZrO on bottom electrode 3 A film;
s3: to PbZrO 3 Implanting helium ions;
s4: and preparing a top electrode.
The method for improving the energy storage density of the dielectric film capacitor provided by the invention is to antiferroelectric material PbZrO 3 Implanting helium ions into the PbZrO 3 Lead PbZrO to be in lattice 3 Crystal lattice distortion and destruction of PbZrO 3 Long range order of dipoles in the crystal, between the top and bottom electrodesUnder the action of an electric field of (2), PbZrO 3 The orientation of the dipoles in the crystal is consistent in a short range, so that the crystal has relaxation ferroelectric property, helium ions do not replace atoms of the original lattice position, and PbZrO is greatly improved 3 The saturation polarization value and the breakdown electric field of the capacitor per se, and the dielectric film capacitor with high energy storage density is obtained.
S1, depositing a bottom electrode on a substrate, wherein the substrate is a perovskite-type material, and selecting a suitable substrate to enable the bottom electrode to grow on the substrate, for example, the substrate may be at least one of strontium titanate, lanthanum aluminate, strontium tantalum lanthanum aluminate, and scandate.
The bottom electrode is perovskite type conductive oxide, and the selected bottom electrode needs to ensure PbZrO 3 The antiferroelectric can be epitaxially grown and maintained on the bottom electrode, for example, the bottom electrode can be at least one of lanthanum strontium manganese oxygen, strontium ruthenate, lanthanum nickelate, lanthanum strontium cobalt oxygen, strontium vanadium oxygen, barium manganese oxygen.
Deposition of PbZrO on bottom electrode Using pulsed laser deposition in S2 3 Film to ensure deposition of the resulting PbZrO 3 Has a single crystal structure and less crystal defects, and PbZrO 3 The film has good performance and is beneficial to uniformly injecting helium ions into PbZrO 3 Inside the crystal, if PbZrO 3 The film is a polycrystalline structure, so that helium ions are easily implanted into the interface between crystal grains when the helium ions are implanted. PbZrO 2 3 The thickness of the film is 50-100nm, and if the film is too thin, the leakage current is too large, which is easy to cause heating damage, and if the film is too thick, the miniaturization of the device is not facilitated.
The dose range of the implanted helium ions in S3 is 5 × 10 14 ～5×10 15 ions/cm 2 . The implantation dosage of helium ions should be moderate, and if the dosage is too low, PbZrO should be added 3 The crystal distortion is not enough to break the long-range order of the dipole, and the PbZrO is damaged when the dosage is too high 3 The integrity of the crystal lattice causes amorphization.
The implantation energy of the helium ions in S3 is 11-22 keV. The implantation energy should be moderate, and if the implantation energy is too low, helium ions may not be implanted into the crystal lattice and stay in the PbZrO 3 The crystal grain surface is distributed unevenly; when the implantation energy is too high, helium ions penetrate PbZrO 3 Into the bottom electrode and bottomSubstrate under electrode, not staying in PbZrO 3 Inside.
To PbZrO 3 When injecting helium ions, the incident direction of the helium ions and PbZrO 3 A deflection angle is formed in the main crystal axis direction of the crystal, the probability of collision of helium ions and crystal lattice atoms is increased, the movement direction of the helium ions after collision is more random, and the helium ions are more uniformly distributed in the crystal lattice. Preferably, the deflection angle is 7-10 degrees, if helium ions are injected along the main crystal axis direction of the crystal, the deflection of the helium ions after the helium ions collide with the crystal lattice is small, and the helium ions can enter the inside of the crystal lattice and even penetrate through PbZrO 3 Film, i.e. producing channeling, according to PbZrO 3 The internal crystal structure sets the deflection angle to avoid channeling.
In S4, the top electrode is at least one of Pt, Ag and Cu.
The invention also provides a dielectric film capacitor comprising a top electrode, a bottom electrode and PbZrO 3 A film, the PZO film being located between the top and bottom electrodes;
the PbZrO 3 The film comprises PbZrO 3 Crystal and helium ion, the helium ion is located in PbZrO 3 Inside the crystal.
The dielectric film capacitor can be prepared by the method for improving the energy storage density of the dielectric film capacitor.
The dielectric film capacitor of the invention improves PbZrO 3 The saturated polarization value and the breakdown electric field of the capacitor per se obtain the dielectric film capacitor with high energy storage density, the preparation process is stable and controllable, and the trend of miniaturization and integration of electronic devices is met.
Example 1
S1: depositing a bottom electrode on a substrate, said substrate being STO (001):
the method comprises the following steps of using pulsed laser deposition equipment, wherein the pulsed laser deposition equipment comprises a heater, a growth cavity, a pulsed laser and an optical path system, the heater is used for heating to a set temperature, the growth cavity is used for growing a film, the pulsed laser is used for generating high-power pulsed laser, and the optical path system focuses the pulsed laser on the surface of a target material.
Adhering STO (001) to heater with silver colloid, placing into growth chamber, pumping gas in growth chamber to 8 × 10 at room temperature -4 Introducing pure oxygen below Pa and keeping the oxygen pressure at about 15 Pa.
The bottom electrode is lanthanum strontium manganese oxygen (LSMO for short), a layer of LSMO with the thickness of 50nm is grown to be used as the bottom electrode, the oxygen pressure in the growth chamber is 15Pa, the growth temperature is 690 ℃, and the bottom electrode is heated to the temperature required by growth at the speed of 20 ℃/min; the energy of laser irradiation on the target material is 70mJ, the laser frequency is 8Hz, the distance between the target material and the substrate is 5.5cm, and the growth time is 7min10 s.
S2: depositing a 50nm thick layer of PbZrO on the bottom electrode 3 The film (PZO film for short) is specifically operated as follows:
the temperature is reduced to 560 ℃ at the speed of 10 ℃/min, the oxygen pressure in the growth cavity is 10Pa, the energy irradiated on the target by the laser is 60mJ, the laser frequency is 8Hz, the distance between the target and the substrate is 5.5cm, and the growth time is 3min47 s. After the growth of the PZO film is completed, the film is cooled at a rate of 10 ℃/min under an oxygen atmosphere of 1000Pa, and then taken out at room temperature.
S3: the sample from S2 was placed in an ion implanter and tilted by 7 ° to avoid channeling. Scanning the sample with helium ions, setting the beam size to about 1mm 2 Scanning frequency of 1kHz, and injection amount of 2.5 × 10 15 ions/cm 2 . And obtaining a helium ion implanted sample after implantation. The implantation energy of the helium ions is 11-22 keV.
S4: selecting Pt as a top electrode, putting a sample injected with helium ions into a vacuum cavity of magnetron sputtering equipment, mounting a platinum (Pt) target, and pumping the vacuum degree in the vacuum cavity to 8 multiplied by 10 -4 And (3) depositing with the deposition power of 20W below Pa, introducing argon, introducing the pressure of 0.4Pa, depositing for 1min, depositing a layer of top electrode with the thickness of about 60nm at room temperature, and finishing deposition to obtain the dielectric film capacitor.
The electrical property test is carried out on the prepared dielectric film capacitor, the dielectric film capacitor is prepared into a capacitor in a circular array shape, so that the electrical property test is convenient, and the specific steps are as follows:
placing the dielectric film capacitor on a photoetching machine, and installing a mask plate, wherein the circular array on the mask plate is a shading part, and light cannot pass through the circular array; and after exposure for 30s, soaking the photoresist in a developing solution matched with the photoresist for 2min, then placing the photoresist in deionized water for ultrasonic cleaning for 2min, drying the surface moisture by using a nitrogen gun after cleaning, and further drying the photoresist on a heating plate at 125 ℃ to obtain a photoresist circular array sample with the diameter of 20 microns.
Placing a photoresist circular array sample in a vacuum cavity of an ion etching device, pumping the vacuum degree in the cavity to be below 8 multiplied by 10 < -4 > Pa, introducing argon, electrolyzing the argon by anode current of 2.5A to generate argon ions to bombard the surface of the sample, and removing Pt which is not covered by the photoresist by etching for 70 s.
And putting the etched photoresist circular array sample into acetone for ultrasonic cleaning for 2min, and removing the residual photoresist on Pt to obtain the circular array capacitor with the diameter of 20 mu m.
This example 1 also provides a dielectric thin film capacitor comprising a top electrode, a bottom electrode and PbZrO 3 A film, the PZO film being located between the top and bottom electrodes; the PbZrO 3 The film comprises PbZrO 3 Crystal and helium ion, the helium ion is located in PbZrO 3 Inside the crystal.
The size of helium ions is much smaller than that of PbZrO 3 The size of the medium atoms and the helium ions are inert particles, and are not easy to generate chemical bond connection with other particles, so that the PbZrO is converted into PbZrO 3 When helium ions are implanted, helium ions are not easy to replace atoms on the original crystal lattice, but are embedded in the crystal lattice, and the crystal lattice is distorted.
X-ray diffraction on dielectric thin film capacitors, as can be seen from FIG. 2, and PbZrO which had not been implanted with helium ions 3 (abbreviated as PZO), 004 crystal plane [ PZO ] in PZO crystal not implanted with helium ions O (004)]The characteristic peak 2 theta of the PZO crystal is 43.92 degrees, and the characteristic peak of the 004 crystal face of the PZO crystal after helium ions are injected is shifted to the left, which shows that the crystal lattice is expanded due to the injection of the helium ions, and the crystal lattice of the PZO crystal is distorted; when the amount of helium ions injected is low, the characteristic peak of the 004 crystal plane of the PZO crystal after helium ions are injected is shifted to the left, and when the amount of helium ions injected is large, the lattice distortion is causedTo a greater extent, from the original orthorhombic phase to the tetragonal phase, the 240 crystal plane [ PZO ] in the orthorhombic phase O (240)]And 004 crystal face [ PZO O (004)]Combine to form the 002 crystal face [ PZO ] in the tetragonal phase T (002)]，PZO T (002) 2 θ becomes 43.27 °.
As shown in fig. 3, the initial sample was a PZO thin film, which was not implanted with helium ions. The polarization value and the area enclosed by the polarization value and the electric field are in positive correlation with the energy storage density, the energy storage density of the dielectric film capacitor prepared in the embodiment 1 is higher than that of the initial sample, and the energy storage density is 62.25J/cm 3 。
As shown in fig. 4, after the helium ions are injected into the PZO film, the breakdown electric field of the dielectric film capacitor is larger than that of the initial sample, and the dielectric film capacitor can withstand higher voltage, is not easily damaged, and can have higher energy storage density.
As shown in fig. 5, i represents the sample of the ith test, n is the total number of samples, pi ═ i/(1+ n), β is the slope, α is the scaling parameter, E represents the breakdown strength, and the breakdown probability of each sample is:
E BDS the breakdown strength obtained by weighting each sample is improved after injecting helium ions into the PZO film, and the dielectric film capacitor can bear higher breakdown strength and is not easily damaged under high voltage.
Example 2
The technical scheme of this embodiment 2 is similar to that of embodiment 1, and the main difference technical features are as follows:
s2 deposition of a 100nm thick layer of PbZrO on the bottom electrode 3 A film.
In S3, the sample obtained in S2 was placed in an ion implanter and tilted by 10 ° to avoid the channeling effect and the implantation dose of helium ions was 5 × 10 15 ions/cm 2 . The implantation energy of helium ions is 11 keV.
For the prepared dielectric film capacitorPerforming electrical property test, and measuring the energy storage density to be 41J/cm 3 。
Example 3
The technical scheme of this embodiment 3 is similar to that of embodiment 1, and the main difference technical features are as follows:
s2 deposition of a 50nm thick layer of PbZrO on the bottom electrode 3 A film.
The implantation dose of helium ions in S3 is 5 × 10 14 ions/cm 2 . The implantation energy of helium ions was 22 keV.
The prepared dielectric film capacitor is subjected to electrical property test, and the energy storage density is measured to be 17.38J/cm 3 。
The present invention is not limited to the above-described embodiments, and various modifications and variations of the present invention are intended to be included within the scope of the claims and the equivalent technology of the present invention if they do not depart from the spirit and scope of the present invention.
Claims (6)
1. A method for improving the energy storage density of a dielectric film capacitor is characterized in that:
the method comprises the following steps:
s1: preparing a bottom electrode;
s2: deposition of PbZrO on bottom electrode 3 A film;
s3: to PbZrO 3 Injecting helium ions; the dose range of implanted helium ions is 5 × 10 14 ～5×10 15 ions/cm 2 (ii) a The implantation energy of helium ions is 11-22 keV; incident direction of helium ion and PbZrO 3 The main crystal axis direction of the crystal forms a deflection angle which is 7-10 degrees;
s4: preparation of a top electrode, said PbZrO 3 A membrane is positioned between the top and bottom electrodes.
2. A method of increasing the energy storage density of a dielectric thin film capacitor as claimed in claim 1, wherein:
PbZrO 3 the thickness of the film is 50-100 nm.
3. A method of increasing the energy storage density of a dielectric thin film capacitor as claimed in claim 1, wherein:
the bottom electrode is a perovskite type conductive oxide.
4. A method of increasing the energy storage density of a dielectric thin film capacitor as claimed in claim 1, wherein:
in S1, a bottom electrode is deposited on a substrate, the substrate being a perovskite-type material.
5. A method for increasing the energy storage density of a dielectric thin film capacitor as claimed in any one of claims 1 to 4 wherein:
deposition of PbZrO on bottom electrode Using pulsed laser deposition in S2 3 A film.
6. A dielectric thin film capacitor prepared by the method for increasing the energy storage density of the dielectric thin film capacitor according to any one of claims 1 to 5, wherein:
comprises a top electrode, a bottom electrode and PbZrO 3 Film of PbZrO 3 A thin film is positioned between the top electrode and the bottom electrode;
the PbZrO 3 The film comprises PbZrO 3 Crystal and helium ion, the helium ion is located in PbZrO 3 Inside the crystal.
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