Towards room-temperature deterministic ferroelectric control of ferromagnetic thin films

Zhen Huang
EPFL, 2015
Thèse EPFL

Résumé

The persisting demand of higher computing power and faster information processing keeps pushing scientists and engineers to explore novel materials and device structures. Within emerging functional materials, there is a focus on multiferroics materials and material-systems possessing both ferroelectric and ferromagnetic orders. Multiferroics with two order parameters coupled through a magnetoelectric interaction are of particular interest for novel information processing technologies. This thesis explores a promising concept of magnetoelectric multiferroic heterostructure incorporating separate ferroelectric and ferromagnetic thin layers with field-effect-mediated coupling through the heterointerface. The major issues related to ferroelectric control of ferromagnetism in multiferroic heterostructures addressed in this thesis include non-volatile magnetoelectric coupling at room temperature, deterministic switching of magnetization via polarization reversal, ferroelectric control of dynamics of magnetic domains and integration of ferroelectric gates on magnetic channels. The major accomplishments of this thesis are the following: Non-volatile ferroelectric control of magnetic properties has been demonstrated in ultra-thin Co layers at room temperature. The ferromagnetic transition Curie temperature, magnetic anisotropy energy and magnetic coercivity are shown to be switchable via the persistent field effect associated with the ferroelectric polarization. The magnitude of the effect is comparable or exceeds the results observed using the conventional (non-ferroelectric) gates. Local control of individual magnetic domain nucleation and propagation in Co channels by creating new ferroelectric domains has been achieved at the ambient conditions. The microscopic ferroelectric domains written on poly(vinylidene fluoride-trifluoroethylene) [P(VDF-TrFE)] ferroelectric polymer gate projected onto the magnetic channel changing locally the magnetic anisotropy energy, and consequently altering magnetic domain dynamics. Therefore it was possible to promote/impede magnetic domain nucleation and significantly change the domain wall velocity using a non-destructive and reversible procedure of ferroelectric domain writing. Non-volatile control of anisotropic magnetoresistance (AMR) has been demonstrated on diluted magnetic semiconductor (Ga,Mn)(As,P) thin films with integrated P(VDF-TrFE) ferroelectric gate. The field effect induced by the ferroelectric gate has shown the capability to strongly modulate the AMR behavior. Profound qualitative changes of the nature of AMR has been observed, including complete on/off switching of the crystalline component of AMR in (Ga,Mn)(As,P). A workflow for fabrication of integrated FET-type structures comprising a magnetic metal or semiconductor magnetic channel and ferroelectric polymer gate has been successfully developed. Different approaches for enhancement of ferroelectric gate operation were explored including integration of highly resistive hydrophobic interfacial layer and change of polymer composition for lower leakage. A significant increase of the non-volatile gate effect magnitude compared to the state of art was reached via improved quality of the ferroelectric/ferromagnetic interface.

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https://infoscience.epfl.ch/record/214611?ln=fr

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Zhen Huang
EPFL, 2015
Thèse EPFL

Résumé

Official source

https://infoscience.epfl.ch/record/214611?ln=fr

À propos de ce résultat

Concepts associés (25)

Concepts associés

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Publications associées (93)

Publications associées

Chargement

Ferroelectric Polymer Gates for Persistent Field Effect Control of Ferromagnetism in (Ga,Mn)As Layers

Sebastian Riester

The growing demand for higher computing power and element density continuously drives the development of novel device concepts. One group of materials currently attracting a lot of interest are the magnetoelectric multiferroics, due to their potential for creating devices with novel functionalities. These materials exhibit coupled ferroelectric and ferromagnetic behavior. Although the focus is on homogeneous multiferroics like bismuth ferrite, the stronger multiferroic coupling that is possible in composite multiferroics makes them attractive for many potential applications (e.g. spintronic logic and memory elements). In particular, electric field-mediated multiferroic composites promise worthwhile compatibility with CMOS circuitry. The present work explores a multiphase multiferroic system where the ferroelectric gate controls a dilute magnetic semiconductor (DMS) channel via the nonvolatile field effect associated with the spontaneous polarization. The system consists of a copolymer of vinylidene fluoride and trifluoroethylene [P(VDF-TrFE)] as the ferroelectric gate and an ultra-thin magnetic layer of (Ga,Mn)As which is one of the most well-established DMS and is considered a chief candidate for spintronic applications. The main outcomes of this research can be summarized as follows: A widely recognized incompatibility between ferroelectrics and group III-V semiconductors has been solved by the integration of a polymer ferroelectric onto a DMS in a multiferroic transistor configuration. Nonvolatile electric field control of ferromagnetism in a (Ga,Mn)As channel has been successfully demonstrated. Several pieces of evidence including the change of hysteretic properties, ferromagnetic Curie temperature shift and magnetoresistance behavior attest to the field effect-mediated multiferroic coupling in this system. Low ferroelectric gate operation voltages below 10 V were achieved through aggressive P(VDF-TrFE) thickness reduction without diminishing the gate effect strength. Polarization screening at the semiconductor/ferroelectric interface was identified as the main issue limiting the ferroelectric gate effect. A significant enhancement of the multiferroic coupling has been reached by thinning the (Ga,Mn)As channel down to 3 nm without compromising the ferromagnetic properties. From the Curie temperature response to ferroelectric gating, that follows the same trend for samples with thicknesses ranging from 3 to 7 nm, we conclude that the 2D limit has not been reached for the thinnest channels and the 3D models describing the ferromagnetic coupling are valid for this case. The ferroelectric control of ferromagnetism has been quantitatively interpreted in terms of existing models for hole-mediated exchange in (Ga,Mn)As.

EPFL2010

Chargement

Patterned and self-assembled ferroelectric nano-structures obtained by epitaxial growth and e-beam lithography

Simon Bühlmann

The continuous downscaling of microelectronic circuits combined with increasing interest in ferroelectric thin films for non-volatile random access memories (FeRAM) is drawing great attention to small ferroelectric thin film structures. There are various challenges and open questions related to processing and theoretical understanding. The processing must assure damage-free ferroelectric capacitors of reproducible properties. More theoretical understanding is necessary to estimate the impact of size effects on the stability of the ferroelectric polarization, domain configurations, switching properties, and other properties such as the piezoelectric response. Pb(Zr,Ti)O3 (PZT) is one of the favorite materials for FeRAMs. Today's capacitors are poly-crystalline with sizes in the micron range. Each capacitor is composed of a large number of grains, guaranteeing the averaging of electrical properties. If only a few grains were present, the scattering of properties from one capacitor to another would take place. This can be avoided using oriented single-crystalline capacitors. An important processing issue is patterning. The switchable polarization might be reduced due to etching damage, a frequently reported current fabrication problem. There is also the question of domain configuration - processing relations. The optimal solution of (001) oriented tetragonal PZT cannot be realized in large capacitors because ferroelastic 90° domains form spontaneously upon cooling through the transition temperature and are stabilized for reasons of stress compensation. In this work, we investigated two routes to fabricate small ferroelectric structures: A subtractive route and an additive route. Patterning was done by electron beam lithography (EBL) in order to access the sub 100nm range. Dry etching was done in an electron cyclotron resonance (ECR/RF) reactor working at very low pressures and ion energy. In the subtractive route, the starting point were continuous 50 to 200nm thick Pb(Zr0.4,Ti0.6)O3 films, which were deposited on conductive, Nb-doped SrTiO3 (100) substrates. The films were c-axis oriented with an a-axis fraction of about 20%. The films were patterned by means of EBL. The positive poly-methyl-methacrylate (PMMA) resist was spun on the PZT film, a dot pattern was directly written by the e-beam, and after development a Cr layer was evaporated. The obtained Cr patterns served as a hard mask for PZT dry etching. Features with an aspect ratio of up to 2 could be cut out of a 200nm thick PZT film. We have shown that dry etching in an electron ECR/RF reactor provides damage-free single crystalline sub-200nm features which were still ferroelectric. The smallest features obtained had a lateral size of 80nm. We found that the resolution of the EBL was limited by the backscattering of electrons from the high density PZT layer. Piezoelectric sensitive atomic force microscopy (PAFM) revealed an increase in the piezoelectric response when the feature's aspect ratio was increased. The measured piezoelectric coefficient increased by a factor of more than three compared to the continuous film. Un-clamping was found to account only for a portion of the increase. As major contribution, we suppose a change in the domain configuration from a to c, and unpinning of domains. This hypothesis was supported by local PAFM measurements on the continuous film, where the same behavior was observed, when the film underwent local training cycles just before the measurement using pulses with voltages well above the coercive field. It is also important to investigate non-destructive fabrication processes to reduce the negative impact of interface defects and grain boundaries. This was achieved using an additive route. The fact, that PZT nucleation on Pt surfaces is difficult but easy on TiO2 was used for the site controlled growth of PZT single crystals on patterned 2nm thick TiO2 layers serving as affinity spots. This route was carried out on Pt (111) and (100) surfaces. A 50nm thick Pt layer was epitaxially grown on single crystalline SrTiO3 (111) and MgO (100) substrates, and then covered by a 2nm thick TiO2 layer. On both substrates, the TiO2 was found to be (100) oriented. In this route, EBL was used to pattern the TiO2 layer into seed islands. As only 2nm of TiO2 layer have to be etched, a new type of negative organic mask could be used, which circumvented the lift off process. Direct deposition of Pb(Zr0.4,Ti0.6)O3 on the seed island covered Pt (111) surfaces led to the nucleation of triangular shaped crystals only on the seeds and not elsewhere. The lateral size of the triangles was between 30 and 150nm. The uniform orientation of the triangle's sidelines implies epitaxial growth of the PZT. Applying a 1nm thick PbTiO3 starting layer prior to PZT deposition increased the nucleation density. A 2nm thick PbTiO3 starting layer prior to PZT deposition led to square shaped crystals on small TiO2 seeds implying the growth of (001) PZT. On Pt, triangular crystals were obtained. For this deposition, the squares showed a uniform size distribution, but their in-plane orientation was random. In all cases, the nucleus density was found to be 60 times less on Pt than on the affinity spots. The nucleation controlled character was expressed in an observable depletion layer around larger TiO2 seeds. A theoretical nucleation model was able to well explain this behavior and the relevant parameters such as activation energies of diffusion and desorption could be derived from experiments. On the Pt (100) surface, direct deposition of PZT led to the nucleation of a non-ferroelectric phase on most parts of the substrate. A depletion around TiO2 seeds was again observable. PZT crystals were found exclusively on some TiO2 seeds. PAFM measurements revealed that all PZT crystals obtained by the additive route were ferroelectric. The ferroelectric features have been investigated by means of PAFM. Complex domain structures were identified, the smallest observed domains had diameters of 15nm. The thinnest investigated feature showing ferroelectricity was 6nm thick. An attempt was made to compare experimental findings with the Landau-Devonshire-Ginzburg phenomenological theory. The d33,f loop together with the CV-loop of a 600nm thick, mostly c-oriented film could well be described by the theory. Deviations could be identified as domain wall contributions. The critical thickness for ferroelectricity was estimated using in addition literature data for domain wall energies. The critical thickness was calculated as 1 to 2nm, which does not contradict experimental findings.

EPFL2004

Chargement

Ferroelectrics are characterised by a spontaneous polarisation that can be reversed by an external electric field. The stability of the polarisation states and the possibility for controlled switching between the states render ferroelectric materials very attractive for memory applications, in which polarisation states are associated to a binary information "0" or "1". Fast, dense, and reliable data storage has gained enormous importance in our information technology based society. In this context, the fundamental physics of ferroelectric materials attracted great interest with the ultimate goal of reaching memory elements with shortest access times and highest densities. Two model systems of ferroelectric materials were studied in this thesis on the polarisation reversal: an inorganic, classical perovskite and an organic polymer. Despite the fundamental structural differences between lead zirconate titanate [Pb(Zr,Ti)O3] and the investigated polyvinylidene fluoride-trifluoroethylene [P(VDF-TrFE)] copolymer, the switching kinetics in these materials can be described by a similar formalism. Our approach of a combination of macroscopic and microscopic techniques enables an insight into the mechanisms of the polarisation reversal and allows for a better understanding of macroscopic effects governed by mechanisms occurring on the nanoscale. The experimental techniques developed for the ferroelectric capacitor structures have been successfully applied for studying a first hybrid PVDF/silicon ferroelectric transistor for non-volatile information storage. The major accomplishments of this thesis are the following: We demonstrated for the first time a piezoelectric scanning probe study on the cross section of ferroelectric thin films. In combination with switching pulses, this allowed us to directly image the polarisation reversal in ferroelectric films quasi-dynamically. The utility of cross-sectional domain imaging as a powerful tool for the study of the polarisation reversal in ferroelectrics has been corroborated. The apparent contradiction between observations interpreted as a fast sideways growth and the classical scenario of a fast forward growth could be explained by an oblique polarisation direction with respect to the film plane. A surface-stimulated nucleation of reverse domains, with preference on the electrode with a negative potential was observed. It was interpreted in terms of a built-in field due to a depletion layer at the ferroelectric-electrode interface. A combination of microscopic and macroscopic methods used for the first time in organic ferroelectric thin films enabled a better insight into polarisation reversal of the copolymer of vinylidene fluoride and trifluoroethylene P(VDF-TrFE). The polarisation reversal was found to be impeded by a restricted domain growth. This limits the applicability of the conventional Kolmogorov-Avrami model as well as the nucleation-limited switching model with a broad distribution of nucleation times. We demonstrated that an interface-adjacent passive layer may impact on the switching properties and gives rise to a retardation of the polarisation reversal. Furthermore, an extraordinary dielectric constant increase was observed in the films with a passive layer due to an additional domain wall contribution. We fabricated for the first time a hybrid silicon/ferroelectric polymer ferroelectric single transistor memory element with non-volatile operation. The observed difference of the polarisation reversal kinetics of the ferroelectric in the simple capacitor and in the transistor structure was explained by the gate oxide buffer layer in the transistor. Our previously developed tools and approaches enabled a better understanding of retention loss mechanism. A semi-quantitative retention model was suggested that explains the observed exponential retention loss. The investigation of relevant fundamental aspects of ferroelectric materials and the development of novel characterisation techniques in this work can be of interest for further development of non-volatile memory devices.

EPFL2008

Chargement

Ferroelectric Polymer Gates for Persistent Field Effect Control of Ferromagnetism in (Ga,Mn)As Layers

Sebastian Riester

EPFL2010

Patterned and self-assembled ferroelectric nano-structures obtained by epitaxial growth and e-beam lithography

Simon Bühlmann

EPFL2004

EPFL2008