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# Self-assembled monolayers of push-pull chromophores as active layer and their applications

Junlong Wang, Virginie Gadenne, Lionel Patrone, Jean-Manuel Raimundo

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Junlong Wang, Virginie Gadenne, Lionel Patrone, Jean-Manuel Raimundo. Self-assembled monolayers of push-pull chromophores as active layer and their applications. Molecules, 2024, 29 (3), pp.559. 10.3390/molecules29030559. [https://doi.org/10.3390/molecules29030559](https://doi.org/10.3390/molecules29030559)

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# Self-assembled monolayers of push-pull chromophores as active layer and their applications

Junlong Wang<sup>1,2</sup>, Virginie Gadenne<sup>2</sup>, Lionel Patrone<sup>2,*</sup> and Jean-Manuel Raimundo<sup>1,*</sup>

**Abstract:** In recent decades, considerable attention has been focused on the design and development of surfaces with defined or tunable properties for a wide range of applications and fields. To this end, self-assembled monolayers (SAMs) of organic compounds offer a unique and straightforward route of modifying and engineering the surface properties of any substrate. Thus, alkane-based self-assembled monolayers constitute one of the most extensively studied organic thin-film nanomaterials, which have found wide application in antifouling surfaces, control of wettability or cell adhesion, sensors, optical devices, corrosion protection, organic electronics, among many other applications. Some of which have led technological transfer to industry. Nevertheless, recently, aromatic-based SAMs have gained in importance as functional components, particularly in molecular electronics, bioelectronics, sensors, etc., due to their intrinsic electrical conductivity and optical properties, opening up new perspectives in these fields. However, some key issues affecting device performances still need to be lifted off to ensure their full use and access to novel functionalities such as memories, sensors, or active layers in optoelectronic devices. In this context, we will present herein recent advances of π-conjugated systems-based self-assembled monolayers (e.g., push-pull chromophores) as active layer and their applications.

**Keywords:** self-assembled monolayers; push-pull chromophores; self-assembly; active layers; optoelectronics.

## 1. Introduction

Self-assembly is a ubiquitous phenomenon in nature, in which building units composed of atoms, (bio)molecules, polymers, colloids or particles are capable of self-organizing into ordered and/or functional patterns or superstructures [1-2]. Self-assembling proceeds randomly or directionally and is governed by local interactions (repulsive or attractive forces) between the monomer units themselves, with or without external direction [3]. Nanoscale self-assembling occurs at interfacial or solution and constitutes the easiest bottom-up approaches [4].

Among these self-assemblies, self-assembled monolayers, classically referred to as SAMs [5-6], constitute an interesting approach for surface functionalization, fine-tune the properties of a surface of interest and are suitable for industry. The concept of SAMs was first introduced at the liquid-gas interfaces [7-8] prior to be reported in the late 40's by Bigelow *et al.* [9-10] then successively by Sagiv *et al.* [11] and Nuzzo *et al.* [12] on substrates and suggested later for applications by Whitesides *et al.* [13]. Due to the wide range of applications of SAMs, the pioneers of the field were awarded in 2022 by the Kavli prize in nanoscience [14]. SAMs are long-range ordered two dimensional single-molecular layers of well-oriented chemisorbed or physisorbed organic compounds, which assemble spontaneously on various surfaces, in the gas phase or in solution. The compounds used for the fabrication of SAMs are generally amphiphilic molecules composed of three parts [15]: (i) the anchoring or head group which interacts and binds to the surface, (ii) a spacer typically a molecular backbone made of aliphatic chain or aromatic oligomer imparting the molecular packing and order, (iii) the end or tail group which is responsible of the surface energy, chemistry, and topography of the outer interface [16-17] (Figure 1).

<footnote n="1">¹ Aix Marseille Univ, CNRS, CINAM, AMUTECH, Marseille, France; jean-manuel.raimundo@univ-amu.fr</footnote>

<footnote n="2">² Aix Marseille Univ, CNRS, IM2NP, AMUTECH, ISEN Yncréa Méditerranée, Toulon, France; lionel.patrone@im2np.fr</footnote>

<footnote>* Correspondence: jean-manuel.raimundo@univ-amu.fr; Tel.: +33 (0) 615 178 793 (J.-M. R.); lionel.patrone@im2np.fr (L. P.)</footnote>
<figure><img src="image_3.png" /><figcaption>**Figure 1.** Amphiphilic self-assembling molecule showing the end group, spacer, and tail group in interaction with a substrate.</figcaption></figure>

Based on the molecular deposition techniques used, uniform homomolecular or heteromolecular SAMs can be obtained at the liquid/liquid, liquid/solid, air/liquid or air/solid interfaces with the existence of two monolayer types namely the Gibbs and Langmuir monolayers [¹⁸⁻¹⁹]. However, the development and performance of such SAMs can be hampered by some hurdles. Indeed, the quality and properties of the SAMs depend on several parameters among them the thickness of the monolayer, the molecular orientation and ordering, the uniformity and coverage, the chemical composition, odd-even effects of the linker [²⁰], electrostatic effects [²¹] the thermal and chemical stabilities [²²]. In addition, several factors affect the SAMs formation [²³] i.e., temperature [²⁴⁻²⁵], immersion time [²⁶], solvent [²⁷⁻²⁸], concentration, humidity and O₂ contains [²⁹⁻³⁰] and need to be mastered and controlled to attain the desired properties.

SAMs based on alkanethiols [¹⁴,³¹], alkanesilanes [³²], alkanecarboxylates [³³], alkanephosphonates [³⁴] etc. on metallic or metal oxides [³⁵] substrates have been extensively studied, both experimentally and theoretically along with the development of novel efficient headgroups such as N-heterocyclic carbenes (NHCs) [³⁶⁻³⁷] or multidentate adsorbates [³⁸]. Indeed, SAMs are a versatile and inexpensive surface coatings that have been used either in a static or dynamic way (by using various stimulus) for a variety of applications including micro- and nanofabrication [³⁹⁻⁴⁰], sensors [⁴¹], batteries [⁴²], biological [⁴³], energy [⁴⁴], electronics [⁴⁵] among many other applications.

Recently an interest to SAMs made from π-conjugated systems have gained a wide attention due to their intrinsic optical and electrical properties, which can be used in molecular electronic devices, molecular (bio)sensors, bioelectronics, photovoltaics and so on [⁴⁶]. For instance, in molecular electronics, these SAMs are commonly used to fine tune the work functions of metallic or inorganic electrodes to minimizing the energy barriers for holes, electrons injection or extraction from an active organic layer [⁴⁷]. Such highly ordered π-conjugated chromophores are also often encountered in nature and act either as photon absorber, electron donor and acceptors (chlorophyll, pheophytins, quinines etc.), or as eye photoreceptors in human retina [⁴⁸] resulting in efficient photoinduced charge separation and electron transfer. Thereby, self-assembling of π-conjugated chromophores constitutes a key-point in organic nanodevices to improve their properties and operation [⁴⁹]. Elaboration of SAMs made from organic π-conjugated molecules will follow the same recipes as described for alkane-based self-assembled monolayers considering additional parameters that could influence the SAMs like the dipole effect [⁵⁰⁻⁵¹], the alkyl spacer influence between the aromatic backbone and surface [⁵²], the number of aromatic rings, and so on.

Π-conjugated systems are versatile organic materials for optoelectronics whose optical and electrical properties are strongly impacted when self-assembled as thin films [⁵³] and need to be well controlled and oriented to optimize the device performances in which they are implemented [⁵⁴⁻⁵⁵]. Among them, push-pull chromophores (referred classically as donor-π-bridge-acceptor or D-π-A) are a class of peculiar importance [⁵⁶] with various shapes linear, branched, twisted, planar, nonplanar etc. [⁵⁷⁻⁵⁸], exhibiting linear and/or nonlinear optical properties, electrical properties that are useful for instance in the design, conception, and manufacture of electronic devices. However, in most cases these
push-pull chromophores are embedded and used in their final form in polymeric or composite matrixes (as doped or grafted, poled or not) [⁵⁹] and rarely as SAMs. Thus, we will report herein some recent results and applications dealing with push-pull chromophores-based SAMs and their applications.

## 2. SAMs from push-pull chromophores for dye-sensitized solar cell applications

Push-pull chromophores have been extensively studied during last years with the aim to incorporate them within the conception of organic solar cells [⁶⁰], mainly as donor materials. Among various solar cells technology, their use in dye-sensitized solar cells (DSSC) revealed interesting since such donor-π-acceptor (D-π-A) sensitizers exhibit strong molar absorption making it possible to use thin oxide films compatible with the improvement of the open circuit voltage [⁶¹, ⁶², ⁶³, ⁶⁴, ⁶⁵]. Operating principle of DSSC incorporating push-pull assemblies at inorganic oxide surface is depicted in Figure 2 extracted from the recent article of D'Annibale *et al.* [⁶⁶].

<figure><img src="image_4.png" /><figcaption>**Figure 2.** a) Structure of p-DSSCs dye (green: electron donor; violet: π-bridge; red: electron acceptor), b) electron pathway in an illuminated p-DSSCs. From reference [66].</figcaption></figure>

For DSSC good operation, it is mandatory that dyes should be grafted onto the inorganic mesoporous semiconductor oxide film in a controlled organized stacks enabling to determine energy alignments and high charge-transfer kinetics to improve light harvesting [⁶⁷]. Such grafting as SAMs can be carried out using push-pull with adequate anchoring group [⁶⁸] that could be profitably optimized [⁶⁹]. As for incorporating such assemblies within DSSC one can cite for example the work of Gholamrezaie *et al.* [⁷⁰⁻⁷¹] using π-conjugated quinquethiophene derivatives chromophores. Therefore, it is necessary to develop energy-level engineering of chromophores on the metal oxide surface, which can be achieved by the right design of push-pull chromophore through the nature and length of the π-bridge groups, together with using various acceptor and donor groups with different electron affinities. Among the studies on various acceptors one can cite the work of Keremane and co-workers [⁷²] (Figure 3), Paul and Sarkar on PCM-based acceptor [⁷³], and Mustafa *et al.* [⁷⁴] dealing on a theoretical study of the influence of the acceptor nature.

<figure><img src="image_5.png" /></figure>
**Figure 3.** a) Molecular design of D-A new dyes PO1-6 whose studied structures with carboxylic acid anchoring group and different acceptors are presented in b). The benchmark reference dye P1 is shown in c). From reference [72].

Donor nature has also been extensively studied for instance with auxiliary methoxy as a donor to improve metal-free organic dyes performance for DSSC [75]. Some works have been devoted to the effect of both donor and π-spacer [76, 77, 78], or solely on the latter for instance with unconventional helical push-pull enabling internal charge transfer leading to good injection into the conduction band of TiO2 [79], or π-bridge extension to decrease the gap and widen the light absorption range [80]. Such spectral absorption broadening has also been obtained by the co-adsorption of two push-pull dyes [81]. Moreover, donor-π-bridge-acceptor (D-π-A) structure represents a convenient configuration for high charge separation rate on the organic sensitizer. In D-π-A molecule, intramolecular charge transfer (ICT) occurs efficiently between the donor and the acceptor parts, and the intramolecular electronic relaxation has been shown to play a role in the injection process [82]. Improvement of the intramolecular charge transfer rate is indeed a key issue to improve DSSC efficiency [83-84]. To fulfill requirement of a broader spectral response, it is also possible to add an internal electron-withdrawing unit within some new donor-acceptor-π-acceptor (D-A-π-A) dyes by further grafting benzothiadiazole, benzotriazole, diketopyrrolopyrrole, or quinoxaline to the usual D-π-A structure. For instance, Demirak et al. [85] worked on a novel unsymmetrical push-pull sensitizers based on triarylamine-substituted quinoxaline push-pull dyes with the aim to improve the performance of DSSC. Furthermore, such a strategy can also be completed by proper choice of side chains. Indeed, unsymmetrical push-pull porphyrazine have also been reported by Fernandez-Ariza et al. [86]. With the aim to improve absorption features of porphyrins and phthalocyanines, the authors proposed a molecule with a phthalocyanine core incorporating a specific design of the peripheral substituents (Figure 4), thus enabling increased absorption in the red, improved solubility and the possibility to tune the electronic parameters. With such a seminal molecule they obtained a PCE of 3.42% and opened the way to the improvement of panchromatic light harvesting by tuning properly the peripheral functions.

<figure><img src="image_6.png" /></figure>

**Figure 4.** Chemical structures of Pc TT1 and Pz TT112 porphyrazine-based sensitizers and IPCE measured with TT112, from Reference [86]

Particularly, in a more recent work they studied the effect on tuning of the electron-donating unit of push-pull porphyrazines [87] (Figure 5) showing its effect on both adsorption and electron injection processes thus highlighting the design of porphyrazine is a delicate process with strong effect on the electronic properties of the organic dyes and therefore on the DSSC functioning.

<figure><img src="image_7.png" /></figure>
**Figure 5.** Chemical structures of A3B panchromatic push-pull porphyrazines studied in reference [87] still incorporating the electron-withdrawing B moiety of T112 presented in Figure 4, but with subunits made of pyrrole rings substituted with different donor groups.

Playing on the structure of the push-pull has been studied on other several chromophores such as distyryl boron dipyrromethenes as near-infrared sensitizers [88] exhibiting a wide absorption range from UV-visible to near infrared. Interestingly the authors also demonstrated that the size of the TiO2 nanoparticles is also a parameter to tune according to the molecular size of the dye to improve the DSSC performance. As seen with porphyrazine example, macrocycle-based push-pull chromophores such as phthalocyanines [89–90, 91] (Figure 6) and porphyrins [92–93, 94] are good candidates for being used as organic dyes within DSSC and have been extensively studied during the last decades.

<figure><img src="image_8.png" /><figcaption>**Figure 6.** Asymmetric CuPc synthesized and scheme of phthalocyanine (ZnPc) based DSCC. From reference [91].</figcaption></figure>

Concerning porphyrins, push-pull type porphyrin-based dyes have shown the best results [95–96, 97–102] and notably with such compounds Grätzel *et al.* managed to obtain an efficiency of about 13% [103, 104]. Panagiotakis *et al.* [105] have reported increased efficiency with PCE ranging from 5 to 7.6% using carefully designed zinc porphyrin push-pull derivatives grafted via cyanoacrylic acid on TiO2. Particularly they showed using a π-conjugated spacer between the chromophore and the anchoring group enhanced electron transfer and hindered undesirable aggregation on TiO2 surface. Cheema *et al.* [106] have obtained near-infrared absorption by conjugating the porphyrin to indolizine as planar strong electron donor thus inducing π-π interactions such as head-to-tail dye aggregation (Figure 7).

<figure><img src="image_9.png" /><figcaption>**Figure 7.** Indolizine-Porphyrin Push-Pull Dye proposed in reference [106] and evidence of its absorption in the near-infrared.</figcaption></figure>

As for phthalocyanines, they exhibit very good photo- and electrochemical stability and high light harvesting capability in the red/NIR spectral regions [89]. Interestingly, the optoelectronic properties of phthalocyanines can be tuned through the proper choice of the organic substituents around the core, since it has a direct impact on the HOMO-LUMO energy levels as well as on the electron density, but
also by the metalation nature of the core to reach long-living excited states. As it is the case for porphyrin-based DSSC, it is necessary to avoid phthalocyanine aggregation at the oxide surface. Because phthalocyanines easily exhibit aggregation at titania surface, Milan et al. studied unsymmetrically substituted push-pull Zn phthalocyanines on original SnO₂-based DSSC [¹⁰⁷].

### 3. SAMs of push-pull chromophores to improve perovskite solar cell performances

Beside DSSC which represents the main solar cell type incorporating push-pull self-assembly, recent works have also been reported with beneficial use of push-pull chromophores within perovskite solar cells. Indeed, in addition to energy band alignment and improvement of electron transfer at the interface such solar cells undergo a drastic lack of stability and push-pull chromophores have been shown to be able to address all these critical issues. Liu and co-workers have designed an acceptor-donor-acceptor chromophore as an interfacial organic layer whose push-pull effect promotes the charge transfer between organic and inorganic layers in 2D perovskite solar cells by lowering the bandgap of the organic spacer of the perovskite [¹⁰⁸]. The push-pull is made of dithienyl diketopyrrolopyrrole (DPP-2T) with two ammonium cations attached onto both sides of the DPP unit, thus allowing hydrogen bonds with inorganic [PbI6]4- sheet within the perovskite cell. Incorporating such DPP-2T push-pull enables to improve the current (Figure 8) and the performance of the cell with a PCE as high as 18.6%.

<figure><img src="image_10.png" /><figcaption>**Figure 8.** Hole and electron current measured on perovskite solar cell showing higher values for the cell incorporating DPP-2T push-pull. From reference [108].</figcaption></figure>

Still within the use of push-pull as interfacial layer, the push-pull nature has also been exploited with layer deposition on top of the metal oxide to improve electron injection from the photoactive absorber to the metal oxide resulting in the enhancement of the device photocurrent. For example, Gkini and coworkers [¹⁰⁹] have successfully used bodypi-porphyrin dyad with this aim, but with a spin-coated layer. Regarding the key issue of passivation and stability improvement of perovskite cells, some studies have also shown the successful use of push-pull SAM. For instance, bi-phenyl-based SAMs have been successfully used recently as an interfacial layer between ZnO electron transport layer and CH₃NH₃PbI₃ hybrid perovskite to improve their stability [¹¹⁰] as shown in Figure 9.
<figure><img src="image_11.png" /><figcaption>**Figure 9.** Interfacial SAM between ZnO electron transport layer and perovskite (left) and their effect on the solar cell stability (right). From reference [110].</figcaption></figure>

Alagumali and co-workers [111] highlighted the role of push-pull in passivation of the defects within perovskite active materials. Indeed, they used push-pull D-π-A organic small molecule to passivate the undercoordinated Pb<sup>2+</sup> defects, and to both align the bands and increase hydrophobicity which results in the improvement of the solar cell stability by hindering moisture effect (Figure 10).

<figure><img src="image_12.png" /><figcaption>**Figure 10.** Scheme of the push-pull incorporation within perovskite materials, induced band alignment, and evidence of the increase of open circuit voltage and hydrophobicity. From reference [111].</figcaption></figure>

Still with push-pull compounds attached to the perovskite material, Liu et al. [112] addressed the passivation issue. With this aim, they used 3D polydendate complexing agents to achieve defect passivation and crystal growth modulation. The 3D complexing agents are phytic acid (PA) and phytate dipotassium (PAD), and the core of PA material is a six-membered carbon ring surrounded by six phosphate groups which have been shown to perform 3D structural stability for PA materials. The six branches of the PA material undergo multiple chemical complexation which results in 3D skeleton templates enabling passivate defects and regulate perovskite crystallization. Another example of passivation is presented in the article by Zhang et al. [113] where they used polyaromatic molecules based on naphthalene-1,8-dicarboximide (NMI) (Figure 11) and perylene-3,4-dicarboximide (PMI) with different molecular dipoles.
<figure><img src="image_13.png" /><figcaption>**Figure 11.** Scheme of the different chemical passivation functions of 4OH-NMI with corresponding defects in perovskite. From reference [113].</figcaption></figure>

It is shown that such push-pull chromophores provide passivation of defects and, notably, NMI enables energy band alignment. Particularly, NMI passivation leads to the reduction of grain boundaries (Figure 12) and the defect density about three times which allows to reduce non radiative recombination rate and to increase the carrier lifetimes, thus resulting in an increase of nearly 24% of the perovskite solar cell efficiency (PCE).

<figure><img src="image_14.png" /><figcaption>**Figure 12.** Thermal admittance spectroscopy images showing the higher grain boundaries reduction for NMI-modified than for PMI modidified perovskite solar cell in comparison to the non-modified cell (control image). From reference [113].</figcaption></figure>

Moreover, NMI-modified perovskite cells exhibit noticeably higher stability upon exposure to $N_2$ as well as oxygen and humidity (Figure 13).

<figure><img src="image_15.png" /><figcaption>**Figure 13.** Stability test of PMI/NMI/non-modified perovskite solar cell upon exposure to $N_2$ atmosphere, and oxygen and 20-30% of relative humidity. From reference [113].</figcaption></figure>

### 4. SAMs of push-pull chromophores as dielectric materials.

Self-assembled monolayer of push-pull is widely used in the design of self-assembled multilayer nanodielectric (SAND). The major applications of these SAND are in capacitors and in gate insulator of OFET. In the past several years, Fachetti's group [114] was an early leader in investigation into special type of self-assembled nanodielectrics (SAND) grown by depositing an alternating $\sigma$ (Alk) and $\pi$ (STB) molecular layers and having an octochlorotrisiloxane derived capping layer to stabilize/planarize the
assembly and to regenerate a reactive hydroxyl surface for subsequent monolayer deposition. (Figure 14).

<figure><img src="image_16.png" /><figcaption>**Figure 14.** Schematic depiction of SAND studied by Fachetti's group. From reference [114].</figcaption></figure>

From capacitance measurements at 10² Hz, they found that these depend on the constituent molecules. The higher value was obtained for Type II (710 nF.cm⁻²), for Type I and III it's 400 and 390 nF.cm⁻² respectively. These results show the importance of the highly polarizable dipolar layer in improving dielectric constant k, and hence increasing capacitance which gives SANDs excellent insulating properties. These structures were integrated as gate dielectrics in both p-type and n-type OFET's [115]. The carrier mobilities are comparable to OFETs obtained with SiO₂ dielectrics but at lower operating voltage allowing to reduce the power consumption of device.

Several groups have shown that the turn on characteristics of Organic Thin Film Transistor (OTFT) are related to the dipole moment of the molecule used in the SAM. The permanent dipole feature of push pull chromophore well oriented into the SAM on the surface generates the formation of an electrostatic potential which modulates the densities of carrier charge in the semiconductor channel. [116-117-118] . In 2012, Salinas *et al* described and correlated the dipole moment of SAM molecules with the threshold voltage of OTFT [119]. They investigated a set of functionalized n-alkane phosphonic acid molecules with various dipole moments that was deposited on a thin aluminum oxide (Al₂O₃) layer to form a hybrid gate dielectric. They show the Vth is shifted from negative to positive values with increasing dipole moment of the SAM molecule. Although he has demonstrated that the polarization of SAM can play an important role on the charge injection into the channel and can therefore impact Vth, other parameters like charge trapping or impurities can also affect it. An optimum interface between dielectrics and semiconductor is fundamental for efficient device function.

A major part of SAND studied in the literature was composed of an alternating monolayer of polarized molecules such as phosphonic acid derivatives of stilbazolium salts and high-k dielectric metal oxide (ZnO₂; HfO₂), deposited on metal or semiconductor substrate. These organic-inorganic assemblies provide high gate capacitances, lower gate leakage currents than inorganic film, limited trapped charges, chemical and thermal stability.

For SAND fabrication, the step requiring annealing and such thermal annealing limits SAND compatibility with many plastic or biocompatible substrates and restricts applications such as in biointegrated electronics. This is associated with the metal oxide layer densification. In this contribution, the growth, nanostructural, and dielectric properties as well as implementation in TFTs of zirconium oxide-based SANDs self-assembled using UV radiation processing to make ZrOₓ thin-film was done by Huang *et al* [120]. The very high UV photon decomposes the metal oxide precursor and significantly densifies the film (vide infra) [121].

The assembly of the PAE layers between the two ZrOₓ is known to enhance the stack orientational stability and durability (Figure 15) [115]. To further enhance the insulating properties, repetition of PAE-ZrOₓ bilayer (self-assembling of PAE in methanol and UV irradiation of ZrOₓ) deposition n times achieves the fabrication of (Zr-SAND)ₙ superlattices, where n = 1 to 4 (Figure 15d).
<figure><img src="image_17.png" /><figcaption>**Figure 15.** (a) Schematic representation of ZrOₓ film fabrication by UV irradiation. (d) Fabrication procedure for UV-densified zirconia self-assembled nanodielectric (UVD-Zr-SAND)ₙ multilayers. (e) Molecular structure of the PEI organic component of SAND. (f) Absorbance spectra of a primer-ZrOₓ-PAE film without the ZrOₓ capping layer before and after irradiation.</figcaption></figure>

An important question in this fabrication process is whether the stilbazolium unit of the PAE layer is affected by exposure to the strong UV irradiation. The data from optical absorption evolution suggest that the overlying ZrOₓ layer stabilizes the PEA layer against UV damage, likely because PAE is not only sandwiched between oxide layers but also chemically locked on them by the chemistry of the chromophore head and tail. Furthermore, in this way the PAE layer is also essentially encapsulated and protected from ambient air. The XPS spectra argues that oxide precursor decomposition by UV irradiation is more effective than thermal annealing. The data indicate that upon UV exposure, the ZrOₓ films become thinner and plausibly denser.

The new UV irradiated Zr-SANDs (UVD-ZrSANDs) were imaged by AFM to quantify surface characteristics. All AFM images are essentially featureless, and such exceptionally smooth surfaces are ideal for the fabrication of back-gated transistor devices where even moderate interface roughness can detrimentally affect TFT properties, such as carrier mobility, and illustrate the precise level of control afforded by the present processing methodology. MIS sandwich structures containing (UVD-ZrSAND)ₙ layers were fabricated. The results indicate that combining UV irradiated ZrOₓ and PAE at room temperature is an efficient route to replace the conventional thermal processing method, thereby realizing high-performance SAND dielectric layers at room temperature.

The molecular dipolar orientation affects thin-film transistor (TFT) threshold and turn-on voltages for devices based on either p-channel pentacene or n-channel copper perfluorophthalocyanine.

Inverted SAND made from inverted PAE units, namely IPAE (Figure 16) [

[122] and affects the principal OTFT parameters relevant to circuit design and fabrication. Note that, although the π-conjugated azastilbazolium cores of PAE and IPAE are identical, there are minor differences in the structures such as larger distance between the phenylphosphonic acid portion and the core (1 atom in PAE and 2 atoms in IPAE) and, more evident, two hydroxylethyl fragments in the latter versus one in the former structure. However, the hydroxyethyl group is not the anchoring point of the chromophore to the surface but is simply used to achieve good chemical adhesion to the overlying ZrOₓ layer. More importantly, it does not drive the self-assembly process as judged from the kinetics of PAE/IPAE absorption, which are governed by the phosphonic acid fragment and are identical for the two systems.
<figure><img src="image_18.png" /><figcaption>**Figure 16.** Dielectric stacks comprising four-chromophore/ZrOₓ layers on top of the ZrOₓ (p-ZrOₓ) primer film. (a) Conventional Zr-SAND with a phosphonate π-electron (PAE) unit. (b) Inverted ZrSAND with an inverted PAE (IPAE) π-unit.</figcaption></figure>

Even if the main structure of the push-pull chromophore is the pyridinium (+) and aromatic amine (-), the two different anchors have different impacts on the electronic density along the molecular backbone. The phosphonic acid is electron-withdrawing and aliphatic alcohol is electron-donating. Thus, the push-pull characteristic is more significant with the case if the phosphoric acid is connected with pyridinium, and aliphatic alcohol is connected with aromatic amine (the case of PAE). And for IPAE, the hypsochromic shift is due to diminished intrinsic electric dipole strength inside the molecule. Specifically, Zr-SAND shifts the threshold and turn-on voltages to more positive values, whereas IZr-SAND shifts them in the opposite direction. Capping these SANDs with -SiMe₃ groups enhances the effect, affording a 1.3 V difference in turn-on voltage for IZr-SAND vs Zr-SAND-gated organic TFTs. Such tunability should facilitate the engineering of more complex circuits. This type of junction metal/SAM/dielectric can also be used to modulate the interface thermal conductance.

Lu et al. [123] demonstrated that, by using PAE or IPAE chromophores and mixtures of the two, as organic linkers between Au and SiO₂ thin films, the interface thermal conductance of the molecular junction can be tuned based on the relative density of the PAE and IPAE chromophores. The PAE chromophore has two CH₂CH₂OH terminal groups compared to one for the IPAE, and these terminal groups control the weak hydrogen bonding between the organic molecule and the Au film. The transition from PAE to IPAE SAMs leads to a 20% decrease in the cross-plane thermal conductance of the junction. Furthermore, the thermal conductance of the mixed PAE-IPAE SAMs (50%:50% molar ratio) is close to a linear combination of the PAE and IPAE SAMs, suggesting that the chromophores act as independent channels for heat conduction.

In the SAND-n samples, on the other hand, we predict that the conductance of the PAE-ZrO₂ contact is enhanced compared to the conductance of the Au-PAE-SiO₂ contacts, possibly due to a stronger chemical affinity between the phosphonic acid headgroup and ZrO₂ compared to SiO₂, in addition to the stronger adhesion between the hydroxylate tail group with ZrO₂ versus Au. Although the cross-plane thermal conductance of the SAND-n decreases monotonically with an increasing number of PAE-ZrO₂ layers, the cross plane thermal conductivity increases with n. Heat buildup at the organic/inorganic interfaces in the SAND-n resulting from the low thermal conductivity of the ZrO₂ layers and the interface thermal resistance at the PAE-ZrO₂ interface can lead to increased temperatures in these films beyond their suitable operational limits, leading to thermoelastic strain and reconfiguration of the PAE molecules.

A new hafnium oxide-organic self-assembled nanodielectric (Hf-SAND) material consisting of regular, alternating π-electron layers of 4-[[4-[bis(2-hydroxyethyl)amino]phenyl]diazenyl]-1-[4-(diethoxyphosphoryl) benzyl]pyridinium bromide (PAE) and HfO₂ nanolayers is reported [124]. The goal of this research is to develop enhanced performance hybrid superlattice dielectrics using alternative oxides as the SAND oxide component. The motivation for extending to hafnia is based on reports indicating differential affinity of phosphonic acids for various oxides versus ZrO₂, along with
$HfO_2$ thermodynamic and surface chemical differences that may beneficially affect the dielectric properties at low process temperatures [125].

Figure 17 shows the fabrication scheme for the new Hf-SAND-n films. Multilayer variants can be prepared by repeating the indicated self-assembly steps in an iterative fashion, where the n index indicates the number of π-electron/$HfO_x$ bilayers grown on top of the initial $HfO_x$ priming layer. The resulting $HfO_x/π$-electron bilayer is then “capped” with a second layer of $HfO_x$ by spin-coating and baking. This process regenerates the metal oxide surface for additional layers (if desired) of phosphonic acid PAE SAM to initiate the next nanodielectric repeat unit.

<figure><img src="image_19.png" /><figcaption>**Figure 17.** (a) Solution-based Hf-SAND self-assembly procedure employed in this study. (b) Schematic of the various Hf-SAND multilayers produced including the corresponding X-ray reflectivity derived thicknesses (Hf-SAND-1, -4) and estimated thicknesses (HfSAND-2, -3).</figcaption></figure>

$Hf$-SAND-n variants ranging from one to four bilayers ($Hf$-SAND-1~4) were imaged by AFM to quantify the surface roughness, conformality, and contiguity. These films exhibiting RMS roughness values ranking from 1.3 Å for a single layer to 1.7 Å for the four-layer variant, highlighting a negligible additional roughness compared to the native Si oxide surface [126]. This modest increase in roughness is consistent with the deposition of additional dielectric layers. The exceptionally smooth surfaces are ideal for the fabrication of back-gated transistor devices where even moderate interface roughness can detrimentally affects TFT properties [127]. To analyse the elemental and chemical composition of the completed $Hf$-SAND multilayers, XPS was employed. It is concluded that the O 1s signal observed after the present 150 °C processing is qualitatively like metal oxide spectra of samples processed at much higher temperatures (300 °C) [128].

In all electronic circuits, it is critical to limit TFT gate dielectric leakage currents for efficient switching and to minimize power consumption during device operation. In the case of the present capacitor structures, $Hf$-SAND-n dielectric layers' leakage is several orders of magnitude lower than that of native $SiO_2$ capacitors (1 A/cm² at ±2 MV/cm) and is comparable to previous reports utilizing either solution phase self-assembly or vacuum deposition dielectric growth techniques, such as ALD [129], which typically afford optimized leakage current densities of ~10⁻⁸ A/cm² or less. The thicker, multilayer $Hf$-SAND variants exhibit significantly lower electric field normalized leakages which should allow larger voltage biasing windows, useful for several transistor applications. A single layer of $Hf$-SAND can achieve a capacitance density greater than 1 µF/cm² (1.1 µF/cm² measured) versus 0.75 µF/cm² for a single layer of Zr-SAND, and 0.71 µF/cm² for the silane-based SAND type II structure reported in the literature [114]. This represents a capacitance enhancement of nearly 50% over current-generation SAND materials and enables microFarad capacitance densities for the first time from a solid-state SAM-metal oxide hybrid dielectrics which is processable at low temperatures in ambient. In the literature, the one used ZrP as the solid support for the PAE SAM showed 700 nF/cm² for 1p-SAND and 520 nF/cm² for 2p-SAND in the accumulation regime (0 to +1.0 V). Figure 18 graphically illustrates
Hf-SAND dielectric trends in terms of capacitance density versus the bilayer n number, inverse capacitance versus n, EOT, and overall dielectric permittivity (k) of Hf-SAND versus thickness. Also note that as n increases, the overall dielectric constant (k<sub>eff</sub>) also increases. This implies that the PAE layer, which is the majority component in subsequent layers, has a larger k than that of the inorganic oxide. This supports the conclusion of Yoon et al [114] that the stilbazolium group has very high permittivity, generally greater than what can normally be achieved with low temperature sol-gel oxides.

<figure><img src="image_20.png" /><figcaption>**Figure 18.** Plots with best fits of Hf-SAND-n MIS properties. (a) Assuming 1/x decay dependence of capacitance density versus Hf SAND layer number n. (b) Inverse capacitance versus layer number linear relationship. (c) Increasing effective dielectric constant *k*<sub>eff</sub> versus layer number n. (d) EOT versus layer number n.</figcaption></figure>

Recently, this type of SAND has been deposited on IGZO semiconductor as the underlying channel layer. This device exhibits impressive electron mobilities (μsat= 19.4 cm2 V⁻¹ s⁻¹) and low threshold voltage (Vth= 0.83 V) compared to the similar device without push-pull layer combined with Hf oxide. [¹³⁰]

**5. Various electrical and photonic properties generated by push-pull chromophores assemblies**

Ordered assembly of push-pull chromophores at surface is mandatory to settle the expected right functionalization property. Obviously, the nature of the linker between the chromophore and the surface plays a key-role on the organization. Hupfer and coworkers [¹³¹] have studied the role of acrylic versus alkylic linker on the supramolecular structure and the optoelectronic properties of tripodal push-pull thiazoles. Although its more insulating property, the alkyl linker has been found to give higher conductivity to the assembly presumably because it promotes more degrees of freedom enabling supramolecular rearrangement upon electrical measurement. There are very few studies on push-pull electrical properties within single push-pull molecule thick junction [¹³²]. Some works dealing with single push-pull junction are noticeable, such as the use of mechanically break junction to study the electrical conductance modification activated by an external electric field, such as resonance features with oligo(phenyleneethynylene) wires with donor–acceptor substitution on the central ring [¹³³], or electrical bistability of Fe<sup>II</sup>-bis-terpyridine push-pull complexes activated by an external electric field which triggers a spin-cross-over transition [¹³⁴] (Figure 19).
<figure><img src="image_21.png" /><figcaption>**Figure 19.** (a) Fe<sup>II</sup>-bis-terpyridine complexes 1–3 as E-field sensitive spin cross-over switching junctions. (b) Scheme of the E-field triggered switching using the distortion of the Fe<sup>II</sup>-pyridine ligand sphere upon applying of a large enough voltage. From Ref [134].</figcaption></figure>

In the literature, self-assembled push-pull chromophores is mainly used to form supramolecular ordered layers. For instance, Li *et al.* [135] have processed layer-by-layer stacking of self-assembled push-pull derivatives to form 2D organic crystals, by layering amphiphilic-like stacking with alternating attractive layers (AL) and repulsive layers (RL) to build supramolecular “push-pull” assemblies within a liquid surface-assisted solution self-assembly strategy (Figure 20). A monolayer (~1.5 nm thick) is made of two outside RLs and a sandwiched AL with such high packing density that, interestingly, the stacks exhibit outstanding photoelectric integrated property, with high mobility, high crystalline state, and superior deep-blue laser characteristics.

<figure><img src="image_22.png" /><figcaption>**Figure 20.** Schematic representation of the 2D amphiphile-like packing layer similar to 2D lipid bilayer in nature (left), and the AL/RL alternate stacks developed (right). From Ref [135].</figcaption></figure>

Organization-dependent photoelectric properties have also been studied on intermolecular charge transfer push-pull derivatives, such as dithiole-nitrofluorene strong push-pull dyads [136]. On such dyad assembly controlled by symmetrical or asymmetrical dipole-dipole interaction, the authors have reported aggregation induced emission, and particularly red-emitting behavior of the well-formed hierarchical micro- and nanostructures which could find interest in OLEDs. Aggregation induced emission enhancement and strong intermolecular charge transfer have also been used within a solution-processed non-doped orange-red emitting multifunctional organic fluorophore made of two terminal attachments of a push-pull moiety separated by a biphenyl free rotor and its copolymers (Figure 21) [137]. Still controlling the interaction, Kim and co-workers have developed 2D single-crystal down-to two monolayers of (2E,2'E)-3,3'-(2,5-difluoro-1,4-phenylene) bis (2-(5-(4-(trifluoromethyl)phenyl) thiophen-
2-yl)acrylonitrile) which exhibit field-effect electron mobility and photoresponsivity of 3.6 × 10³ A W⁻¹ under green light-emitting diode irradiation [¹³⁸]. Such results constitute the first example of green-sensitive 2D organic phototransistors. All these studies point out the role of the organization within self-assembled push-pull multilayers that could be profitably further developed within a self-assembled monolayer strategy.

<figure><img src="image_23.png" /><figcaption>**Figure 21.** Optimized structure of BPPTA & various molecular compositions of BPPTA–fluorene copolymers (top); Absorption spectra in (a) solution, (b) thin film of the copolymer and BPPTA under irradiation at ~360 nm; PL spectra in (c) solution, (d) thin film of BPPTA and the copolymers. From Ref [137].</figcaption></figure>

**6. Conclusions**

In this paper we have reviewed the beneficial use of organized layers of push-pull chromophores to generate photoelectrical and electrical properties, mainly focusing on self-assembled monolayer strategy to arrange push-pull assemblies. Regarding electrical properties, self-assembled monolayers have mostly been devoted to high k dielectric thin layers for possible application towards nanoelectronic devices such as nanotransistors. Push-pull assemblies have also been extensively studied for improving DSSC and perovskite solar cell operation. Within DSSC push-pull assemblies could behave as efficient sensitizers, whereas for perovskite solar cells they have been shown to be able to address the critical issues of energy band alignment, improvement of electron transfer at the interface, and increase of stability as a passivating interfacial layer. At last, some other photo-electrical properties such as high mobility, high crystalline state, and superior deep-blue laser characteristics, bistability,
aggregation induced emission, particularly red-emitting behavior finding interest in OLEDs or green-
sensitive 2D organic phototransistors, have also been shown to arise from ordered assemblies of push-
pull chromophores. In all these studies, beside the intrinsic push-pull properties, their organization
appeared to play a key-point to generate the desired properties. We believe that further developing self-
assembled monolayer strategy in all the above-mentioned fields should even improve the beneficial
effects of push-pull assemblies.

**Author Contributions:** The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. All authors read and gave valuable suggestions on the manuscript. J. W. review, writing, V. G. review, writing, L. P. conceptualization, review, writing, J. M. R. conceptualization, review, writing, editing.

**Funding:** This work was supported by the Centre National de la Recherche Scientifique (CNRS), the ministère de l'Enseignement Supérieur et de la Recherche (MESR). J. W. acknowledges the MESR for his PhD fellowship.

**Institutional Review Board Statement:** Not applicable.

**Informed Consent Statement:** Not applicable.

**Conflicts of Interest:** The authors declare no conflict of interest.

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